Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom

ABSTRACT

Olefin polymerization catalyst systems including a high molecular weight catalyst compound and a low molecular weight catalyst compound, and methods of making same are provided. High molecular weight catalysts include metallocene catalysts and low molecular weight catalysts include non-metallocene compounds including biphenyl phenol compounds. Generally catalyst systems may include less than about 5.0 mol % of the high molecular weight catalyst compound relative to said low molecular weight catalyst. Methods for olefin polymerization including the aforementioned catalyst systems, and polyolefins and products made therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage application under 35 U.S.C. §371for International Application No. PCT/US08/12691, filed on Nov. 12,2008, that claims the benefit of Ser. No. 61/003,181, filed Nov. 15,2007, the disclosures of which is incorporated by reference in itsentirety.

FIELD OF THE INVENTION

The present disclosure relates generally to polymerization catalysts,methods of using and methods of making said catalysts, and polymers andproducts made therefrom. More particularly, the present disclosurerelates to catalyst systems comprising at least two catalyst components,methods of making said catalyst systems, methods for polymerizingolefins using catalyst systems, and polymers, resins, and articles madetherefrom.

BACKGROUND

The use of metallocene compounds in polymerization catalysts, and theuse of metallocene catalysts for polymerization are known. However,there remains an ongoing effort to develop metallocene catalysts,polymerization processes using such catalysts, and polyolefin resins andproducts made therewith, each having advantageous properties andperformance.

There are numerous references discussing metallocene catalyst systemscomprising at least two catalyst components, wherein at least onecomponent is a metallocene catalyst. For example, U.S. Pat. No.4,530,914 discusses a catalyst system for producing polyethylene havinga broad molecular weight distribution using two differentmetallocene-type catalyst compounds having different propagation andtermination rate constants for ethylene polymerization. U.S. Pat. No.4,937,299 is directed to a homogeneous catalyst system of at least twometallocene-type catalyst compounds each having different reactivityratios for use in a single reactor to produce a polymer blend. U.S. Pat.No. 5,470,811 discusses producing polymers having improved productproperties using an isomeric mixture of two or more substitutedmetallocene-type catalyst compounds. EP-A2-0 743 327 discuss the use ofmeso and racemic bridged mixed metallocene-type catalysts compounds toproduce ethylene polymers having improved processability. U.S. Pat. No.5,516,848 relates to a process for producing polypropylene using abridged mono-cyclopentadienyl heteroatom containing compound and anunbridged, bis-cyclopentadienyl containing compound. EP-B1-0 310 734discusses the use of a mixed bridged hafnium and zirconiummetallocene-type catalyst compounds to produce a polymer having broadmolecular weight distribution. U.S. Pat. No. 5,696,045 describes usingat least two different bridged zirconium metallocene-type catalystcompounds to produce propylene polymers having a broad molecular weightdistribution where one of the stereorigid zirconocenes has an indenylligand having a substituent on the six-member ring. EP-B1-516 018describes using two different bridged zirconium metallocene-typecatalyst compounds to produce a broad molecular weight distributionpolypropylene polymer where one of the bridged metallocenes has indenylligands that are substituted in at least the two position. U.S. Pat. No.6,492,472 discusses a catalyst system comprising at least two differentmetallocene compounds, the system comprising a bridged metallocenecatalyst compound and a bridged, asymmetrically substituted, metallocenecatalyst compound useful for producing polymers generally having anarrow molecular weight distribution. U.S. Pat. No. 7,141,632 discussesa mixed metallocene catalyst system including a poor comonomerincorporating metallocene catalyst compound and a good comonomerincorporating metallocene catalyst compound useful in producing a morebroadly separated bimodal polymer composition. U.S. Pat. No. 7,163,906discusses a catalyst composition comprising the contact product of atleast one metallocene compound and at least one organochromium compound.U.S. Pat. No. 7,172,987 discusses a bimetallic catalyst systemcomprising a modified Ziegler-Natta catalyst component and a metallocenecatalyst component useful for producing bimodal polymers, specificallypolyethylene, having a polydispersity of from 12 to 50.

Additionally, there are also references directed to polymerizationprocesses in which two or more polymerization reactors are joined inseries, where one catalyst is used in a first reactor to produce a firstpolymer that is then fed into a second reactor with the same ordifferent catalyst, typically under different reactor conditions. Inthis way, the resulting polymer from a series polymerization process isa combination or blend of two different polymers. These polymer blends,typically, contain a high molecular weight and a low molecular weightcomponent. For example, U.S. Pat. No. 5,665,818 discusses using twofluidized gas phase reactors in series using a transition metal basedcatalyst to form an in situ polymer blend having improved extrudability.EP-B1-0 527 221 discusses a series reactor process usingmetallocene-type catalyst systems for producing bimodal molecular weightdistribution polymer products. However, series or multistage reactorprocesses are expensive and more difficult to operate.

However, there remains a need for catalyst systems with good reactoroperability. There is also a need for catalyst systems for producingbimodal polyolefin compositions. There is even another need in the artfor methods of polymerizing bimodal polyolefin, preferably, in a singlereactor, having good processability. There is yet another need forolefin polymers and polyolefin products having enhanced properties.These and other limitations may be overcome with the catalysts, methods,polymers, and products of the present disclosure.

SUMMARY

The following presents a general summary of some of the many possibleembodiments of this disclosure in order to provide a basic understandingof this disclosure. This summary is not an extensive overview of allembodiments of the disclosure. This summary is not intended to identifykey or critical elements of the disclosure or to delineate or otherwiselimit the scope of the claims. The following summary merely presentssome concepts of the disclosure in a general form as a prelude to themore detailed description that follows.

According to one embodiment there is provided a catalyst systemcomprising a first catalyst compound and a second catalyst compound,wherein said first catalyst compound is a metallocene, and wherein saidsecond catalyst compound has the following Structure I:

wherein M is a Group 4 metal (IUPAC; new notation), for example, M maybe Ti, Zr, or Hf; each R¹ through R⁹ may be any of hydrides, halides,alkyls or aryls, wherein the alkyls or aryls may optionally besubstituted; and X is at least one leaving group, for example, X may beany of F, Cl, Br, I, Me, Bnz, CH₂SiMe₃, or C₁ to C₅ alkyls; andoptionally a cocatalyst.

According to another embodiment there is provided a catalyst systemcomprising a first catalyst compound that when used in a polymerizationreaction produces a first polymer having a weight average molecularweight (Mw) in the range of from 40,000 to 200,000 g/mol, and a secondcatalyst compound that when used in a polymerization reaction produces asecond polymer having an Mw of greater than 1,000,000 g/mol, and acocatalyst compound. Generally the catalyst system when used in apolymerization reaction produces a polymer product comprising said firstand second polymers, wherein said polymer product comprises at least oneof the following properties: (i) a melt strength value greater than6*MI^(−0.6675) and wherein MI is the melt index value of said polymerproduct measured in accordance with ASTM-D-1238-E, (ii) a ratio ofextensional viscosity measured at a strain rate of 1 sec⁻¹, 190° C., andtime=4 seconds to that predicted by linear viscoelasticity at the sametemperature and time of greater than 3, (iii) an activation energy(E_(a)) of less than 7 kcal/mol/K, and (iv) a Mz/Mw ratio greater thanthe Mw/Mn ratio, wherein Mz is the z-average molecular weight of saidpolymer product, Mw is the weight average molecular weight of saidpolymer product, Mn is the number average molecular weight of saidpolymer product; and v) a van Gurp-Palmen plot comprising a positiveslope and possessing a maximum, wherein the van Gurp-Palmen plot is aplot of the phase angle versus the absolute value of the complex shearmodulus determined from dynamic rheology, more particularly, fromfrequency sweeps in the range from 0.01 to 100 rad/s at 190° C.

According to even another embodiment there is provided a method formaking a catalyst system comprising: contacting in a diluent (a) a firstcompound wherein said compound is a metallocene; and (b) a secondcompound having the following Structure I:

wherein M is a Group 4 metal (IUPAC; new notation), for example, M maybe Ti, Zr, or Hf; each R¹ through R⁹ may be any of hydrides, halides,alkyls or aryls, wherein the alkyls or aryls may optionally besubstituted; and X is at least one leaving group, for example, X may beany of F, Cl, Br, I, Me, Bnz, CH₂SiMe₃, or C₁ to C₅ alkyls; and (c) acocatalyst to form the catalyst system.

According to still another embodiment there is provided a method forolefin polymerization comprising: contacting two or more olefin monomerswith a catalyst system under olefin polymerization conditions to createa polyolefin wherein said catalyst system comprises a first catalystcomponent and a second catalyst component, wherein said first catalystcomponent is a metallocene; and wherein said second catalyst componenthas the following Structure I:

wherein M is a Group 4 (IUPAC; new notation) metal, for example, M maybe Ti, Zr, or Hf; each R¹ through R⁹ may be any of hydrides, halides,alkyls or aryls, wherein the alkyls or aryls may optionally besubstituted; and X is at least one leaving group, for example, X is atleast one leaving group, for example, X may be any of F, Cl, Br, I, Me,Bnz, CH₂SiMe₃, or C₁ to C₅ alkyls; and wherein said first catalystcomponent produces polymer having a weight average molecular weight (Mw)in the range of from 40,000 to 200,000 g/mol, and said second catalystcomponent produces polymer having an Mw of greater than 1,000,000 g/mol.

According to even still another embodiment there is provided a methodfor producing polyethylene comprising the steps of: mixing a firstpolyethylene having a weight average molecular weight (Mw) of greaterthan 1,000,000 g/mol together and a second polyethylene having an Mw inthe range of 40,000 to 200,000 g/mol in a solvent to produce a bimodalpolyethylene solution; and precipitating said bimodal polyethylene outof said solution, wherein said bimodal polyethylene comprises at leastone of the following properties: (i) a melt strength value greater than6*MI^(−0.6675), wherein MI is the melt index value measured inaccordance with ASTM-D-1238-E, (ii) a ratio of extensional viscositymeasured at a strain rate of 1 sec⁻¹, 190° C., and time=4 seconds tothat predicted by linear viscoelasticity at the same temperature andtime of greater than 3, (iii) an activation energy (E_(a)) of less than7 kcal/mol/K, and (iv) a Mz/Mw ratio greater than the Mw/Mn ratio,wherein Mz is the z-average molecular weight of said polyethylene, Mw isthe weight average molecular weight of said polyethylene, Mn is thenumber average molecular weight of said polyethylene; and v) a vanGurp-Palmen plot comprising a positive slope and possessing a maximum,wherein the van Gurp-Palmen plot is a plot of the phase angle versus theabsolute value of the complex shear modulus determined from dynamicrheology, more particularly, from frequency sweeps in the range from0.01 to 100 rad/s at 190° C. Generally the step of mixing comprisesdissolving the first and second polymers in the solvent.

According to even yet another embodiment there is provided an ethylenepolymer comprising at least one of the following properties: (i) meltstrength value greater than 6*MI^(0.6675), wherein MI is the melt indexvalue of said polymer measured in accordance with ASTM-D-1238-E, (ii) aratio of extensional viscosity measured at a strain rate of 1 sec⁻¹,190° C., and time=4 seconds to that predicted by linear viscoelasticityat the same temperature and time of greater than 3, (iii) an activationenergy (E_(a)) of less than 7 kcal/mol/K, and (iv) a Mz/Mw ratio greaterthan the Mw/Mn ratio, wherein Mz is the z-average molecular weight ofsaid polymer, Mw is the weight average molecular weight of said polymer,Mn is the number average molecular weight of said polymer; and v) a vanGurp-Palmen plot comprising a positive slope and possessing a maximum,wherein the van Gurp-Palmen plot is a plot of the phase angle versus theabsolute value of the complex shear modulus determined from dynamicrheology, more particularly, from frequency sweeps in the range from0.01 to 100 rad/s at 190° C.

According to still even another embodiment there is provided an articleproduced from an ethylene polymer comprising at least one of thefollowing properties: (i) melt strength value greater than6*MI^(−0.6675), wherein MI is the melt index value of said polymermeasured in accordance with ASTM D-1238-E, (ii) a ratio of extensionalviscosity measured at a strain rate of 1 sec⁻¹, 190° C., and time=4seconds to that predicted by linear viscoelasticity at the sametemperature and time of greater than 3, (iii) an activation energy(E_(a)) of less than 7 kcal/mol/K, and (iv) a Mz/Mw ratio greater thanthe Mw/Mn ratio, wherein Mz is the z-average molecular weight of saidpolymer, Mw is the weight average molecular weight of said polymer, Mnis the number average molecular weight of said polymer; and v) a vanGurp-Palmen plot comprising a positive slope and possessing a maximum,wherein the van Gurp-Palmen plot is a plot of the phase angle versus theabsolute value of the complex shear modulus determined from dynamicrheology, more particularly, from frequency sweeps in the range from0.01 to 100 rad/s at 190° C.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings illustrate some of the many possible embodimentsof this disclosure in order to provide a basic understanding of thepresent disclosure. These drawings do not provide an extensive overviewof all embodiments of this disclosure. These drawings are not intendedto identify key or critical elements of the disclosure or to delineateor otherwise limit the scope of the claims. The following drawingsmerely present some concepts of the disclosure in a general form. Thus,for a detailed understanding of this disclosure, reference should bemade to the following detailed description, taken in conjunction withthe accompanying drawings, in which like elements have been given likenumerals.

FIG. 1 provides a comparison of Van Gurp-Palmen plots of non-limitingexample resins of the disclosure and conventional resins.

FIG. 2 provides a comparison of the melt strengths of non-limitingexample resins of the disclosure and conventional resins having low MI.

FIG. 3 depicts the transient uniaxial extensional viscosity ofnon-limiting example resin 3 of the disclosure as a function of time.

FIG. 4 provides a comparison of the shear thinning characteristics of anon-limiting example resin of the disclosure and a control resin.

FIG. 5 provides a comparison of non-limiting example resins of thedisclosure and conventional resins.

FIG. 6 provides a comparison of Van Gurp-Palmen plots of non-limitingexample resins of the disclosure and a control resin.

FIG. 7 provides a comparison of Van Gurp-Palmen plots of non-limitingexample resins of the disclosure and conventional resins.

DETAILED DESCRIPTION

Before the present compounds, components, compositions, and/or methodsare disclosed and described, it is to be understood that unlessotherwise indicated this invention is not limited to specific compounds,components, compositions, reactants, reaction conditions, ligands,metallocene structures, or the like, as such may vary, unless otherwisespecified. It is also to be understood that the terminology used hereinis for the purpose of describing particular embodiments only and is notintended to be limiting.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an,” and “the” include pluralreferents unless otherwise specified. Thus, for example, reference to “aleaving group” as in a moiety “substituted with a leaving group”includes more than one leaving group, such that the moiety may besubstituted with two or more such groups. Similarly, reference to “ahalogen atom” as in a moiety “substituted with a halogen atom” includesmore than one halogen atom, such that the moiety may be substituted withtwo or more halogen atoms, reference to “a substituent” includes one ormore substituents, reference to “a ligand” includes one or more ligands,and the like.

The present disclosure provides catalyst systems for olefinpolymerization, methods of making and method of using said catalystsystems, and polymer and products made therewith. The catalyst systemsof the disclosure comprise at least two catalyst components—a firstcatalyst compound and a second catalyst compound. The catalyst systemsmay further comprise one or more additional catalyst compounds. Any twoor more catalyst systems of the disclosure may be combined to produce acatalyst system of the disclosure. The terms “mixed catalyst system” and“mixed catalyst” may be used interchangeably herein with “catalystsystem.”

The catalyst systems of the present disclosure comprise a first catalystcomponent that produces generally low molecular weight polyolefin, and asecond catalyst component that produces generally high molecular weightpolyolefin. As known by one of skill in the art, although the precisemolecular weight of a polyolefin produced by a polymerization catalystin a polymerization reaction is dependent upon reaction conditionsincluding, but not limited to, reaction temperature, hydrogenconcentration, and comonomer concentration, catalysts can be describedby the general molecular weight of the polyolefin they produce understandard reactor conditions, or a range of standard reactor conditions.The first catalyst component that produces low molecular weightpolyolefin may be referred to herein as a “low molecular weightcatalyst”. The second catalyst component that produces generally highmolecular weight polyolefin may be referred to herein as a “highmolecular weight catalyst”. It should be understood that the molecularweight is in reference to the polymer produced by the catalyst and notthe molecular weight of the catalyst itself.

As used herein, “low molecular weight” is defined to be a weight averagemolecular weight (Mw) in the range of from about 40,000 to about 200,000g/mol, preferably from about 50,000 to about 180,000 g/mol, morepreferably from about 60,000 to about 175,000 g/mol, and even morepreferably from about 70,000 to about 150,000 g/mol. In one non-limitingembodiment, low molecular weight is about 100,000 g/mol. As used herein,“high molecular weight” is defined as a weight average molecular weight(Mw) greater than about 1 million g/mol, preferably greater than about1.5 million g/mol, even more preferably greater than about 2 milliong/mol, and still more preferably greater than about 3 million g/mol. Inone non-limiting embodiment, high molecular weight is about 5 milliong/mol.

In one non-limiting embodiment of the disclosure, the low molecularweight catalyst component is a metallocene compound, and the highmolecular weight catalyst is a non-metallocene compound. In anothernon-limiting example the low molecular weight component is a Group 15containing compound. In another non-limiting example the low molecularweight component is a phenoxide transition metal composition. In anothernon-limiting example the low molecular weight component is a Group 5 or6 metal imido complex. In another non-limiting example the low molecularweight component is a bridged bis(arylamido) Group 4 compound. Inanother non-limiting example the low molecular weight component is aderivatives of a metallocene or a phenoxide transition metal compositionor a group 5 or 6 metal imido complex or a bridged bis(arylamido) Group4 compound. In another non-limiting example, the low molecular weightcomponent is any combination of metallocene and a phenoxide transitionmetal composition and a Group 5 or 6 metal imido complex and a bridgedbis(arylamido) Group 4 compound.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name.

The terms “compound” and “complex” are generally used interchangeably inthis specification, but those of skill in the art may recognize certaincompounds as complexes and vice versa.

The terms “precatalyst”, “catalyst”, “precatalyst metal compound”,“catalyst metal compound”, “catalyst component” are generally usedinterchangeably in this specification, but those of skill in the art mayrecognize certain precatalysts as catalysts and vice versa.

The terms “monomer” and “comonomer” are generally used interchangeablyin this specification, but those of skill in the art may recognizecertain monomers as comonomers and vice versa.

For the purposes of illustration, representative certain groups aredefined herein. These definitions are intended to supplement andillustrate, not preclude, the definitions known to those of skill in theart. “Optional” or “optionally” means that the subsequently describedevent or circumstance may or may not occur, and that the descriptionincludes instances where said event or circumstance occurs and instanceswhere it does not. For example, the phrase “optionally substitutedhydrocarbyl” means that a hydrocarbyl moiety may or may not besubstituted and that the description includes both unsubstitutedhydrocarbyl and hydrocarbyl where there is substitution.

The term “alkyl” as used herein refers to a branched or unbranchedsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, aswell as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.Generally, although again not necessarily, alkyl groups herein maycontain 1 to about 12 carbon atoms. The term “lower alkyl” intends analkyl group of one to six carbon atoms, specifically one to four carbonatoms. The term alkyl also refers to divalent alkyls such as —CR₂— whichmay be referred to as alkylenes or hydrocarbylenes and may besubstituted with one or more substituent groups or heteroatom containinggroups. “Substituted alkyl” refers to alkyl substituted with one or moresubstituent groups (e.g., benzyl or chloromethyl), and the terms“heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in whichat least one carbon atom is replaced with a heteroatom (e.g., —CH₂OCH₃is an example of a heteroalkyl).

The term “alkenyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one double bond, such as ethenyl,n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, andthe like. Generally, although again not necessarily, alkenyl groupsherein contain 2 to about 12 carbon atoms. The term “lower alkenyl”intends an alkenyl group of two to six carbon atoms, specifically two tofour carbon atoms. “Substituted alkenyl” refers to alkenyl substitutedwith one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkynyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one triple bond, such as ethynyl,n-propynyl, isopropynyl, n-butynyl, isobutynyl, octynyl, decynyl, andthe like. Generally, although again not necessarily, alkynyl groupsherein may have 2 to about 12 carbon atoms. The term “lower alkynyl”intends an alkynyl group of two to six carbon atoms, specifically threeor four carbon atoms. “Substituted alkynyl” refers to alkynylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group intends an alkoxy group having one to six, morespecifically one to four, carbon atoms. The term “aryloxy” is used in asimilar fashion, with aryl as defined below. The term “hydroxy” refersto —OH.

Similarly, the term “alkylthio” as used herein intends an alkyl groupbound through a single, terminal thioether linkage; that is, an“alkylthio” group may be represented as —S-alkyl where alkyl is asdefined above. A “lower alkyl thio” group intends an alkyl thio grouphaving one to six, more specifically one to four, carbon atoms. The term“arylthio” is used similarly, with aryl as defined below. The term“thioxy” refers to —SH.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, linked covalently, or linked toa common group such as a methylene or ethylene moiety. More specificaryl groups contain one aromatic ring or two or three fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, and the like. In particular embodiments, arylsubstituents have 1 to about 200 carbon atoms, typically 1 to about 50carbon atoms, and specifically 1 to about 20 carbon atoms. “Substitutedaryl” refers to an aryl moiety substituted with one or more substituentgroups, (e.g., tolyl, mesityl and perfluorophenyl) and the terms“heteroatom-containing aryl” and “heteroaryl” refer to aryl in which atleast one carbon atom is replaced with a heteroatom (e.g., rings such asthiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc. orbenzo-fused analogues of these rings are included in the term“heteroaryl”). In some embodiments herein, multi-ring moieties aresubstituents and in such an embodiment the multi-ring moiety can beattached at an appropriate atom. For example, “naphthyl” can be1-naphthyl or 2-naphthyl; “anthracenyl” can be 1-anthracenyl,2-anthracenyl or 9-anthracenyl; and “phenanthrenyl” can be1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or9-phenanthrenyl.

The term “aralkyl” refers to an alkyl group with an aryl substituent,and the term “aralkylene” refers to an alkylene group with an arylsubstituent; the term “alkaryl” refers to an aryl group that has analkyl substituent, and the term “alkarylene” refers to an arylene groupwith an alkyl substituent.

The terms “halo” and “halogen” and “halide” are used in the conventionalsense to refer to a chloro, bromo, fluoro or iodo substituent. The terms“haloalkyl,” “haloalkenyl” or “haloalkynyl” (or “halogenated alkyl,”“halogenated alkenyl,” or “halogenated alkynyl”) refers to an alkyl,alkenyl or alkynyl group, respectively, in which at least one of thehydrogen atoms in the group has been replaced with a halogen atom.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a molecule or molecular fragment in whichone or more carbon atoms is replaced with an atom other than carbon,e.g., nitrogen, oxygen, sulfur, phosphorus, boron or silicon. Similarly,the term “heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the term “heteroaryl” refersto an aryl substituent that is heteroatom-containing, and the like. Whenthe term “heteroatom-containing” appears prior to a list of possibleheteroatom-containing groups, it is intended that the term apply toevery member of that group. That is, the phrase “heteroatom-containingalkyl, alkenyl and alkynyl” is to be interpreted as“heteroatom-containing alkyl, heteroatom-containing alkenyl andheteroatom-containing alkynyl.”

“Hydrocarbyl” refers to hydrocarbyl radicals containing 1 to about 50carbon atoms, specifically 1 to about 24 carbon atoms, most specifically1 to about 16 carbon atoms, including branched or unbranched, saturatedor unsaturated species, such as alkyl groups, alkenyl groups, arylgroups, and the like. The term “lower hydrocarbyl” intends a hydrocarbylgroup of one to six carbon atoms, specifically one to four carbon atoms.“Substituted hydrocarbyl” refers to hydrocarbyl substituted with one ormore substituent groups, and the terms “heteroatom-containinghydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which atleast one carbon atom is replaced with a heteroatom.

By “substituted” as in “substituted hydrocarbyl,” “substituted aryl,”“substituted alkyl,” “substituted alkenyl” and the like, as alluded toin some of the aforementioned definitions, is meant that in thehydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, atleast one hydrogen atom bound to a carbon atom is replaced with one ormore substituents that are functional groups such as hydroxyl, alkoxy,alkylthio, phosphino, amino, halo, silyl, and the like. When the term“substituted” appears prior to a list of possible substituted groups, itis intended that the term apply to every member of that group. That is,the phrase “substituted alkyl, alkenyl and alkynyl” is to be interpretedas “substituted alkyl, substituted alkenyl and substituted alkynyl.”Similarly, “optionally substituted alkyl, alkenyl and alkynyl” is to beinterpreted as “optionally substituted alkyl, optionally substitutedalkenyl and optionally substituted alkynyl.”

By “divalent” as in “divalent hydrocarbyl”, “divalent alkyl”, “divalentaryl” and the like, is meant that the hydrocarbyl, alkyl, aryl or othermoiety is bonded at two points to atoms, molecules or moieties with thetwo bonding points being covalent bonds. The term “aromatic” is used inits usual sense, including unsaturation that is essentially delocalizedacross multiple bonds, such as around a ring.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of SiZ¹Z²Z³ is independently selected from the group consisting ofhydride and optionally substituted alkyl, alkenyl, alkynyl,heteroatom-containing alkyl, heteroatom-containing alkenyl,heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino,silyl and combinations thereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is as defined above. As used herein, the term “phosphino”refers to the group —PZ¹Z², where each of Z¹ and Z² is as defined above.As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z², Z³ as defined above. The term “amino” is used herein torefer to the group —NZ¹Z², where each of Z¹ and Z² is as defined above.The term “amine” is used herein to refer to the group: NZ¹Z²Z³, whereeach of Z¹, Z², Z³ is as defined above.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like. The term “unsaturated” refers to the presence of one or moredouble and triple bonds between atoms of a radical group such as vinyl,acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.

Metallocene Catalysts

The catalyst system may include at least one metallocene catalystcomponent. The metallocene catalyst component may include “halfsandwich” and “full sandwich” compounds having one or more Cp ligands(cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to atleast one Group 3 to Group 12 metal atom, and one or more leavinggroup(s) bound to the at least one metal atom. Hereinafter, thesecompounds will be referred to as “metallocenes” or “metallocene catalystcomponents”.

In one aspect, the one or more metallocene catalyst components arerepresented by the formula (I):Cp^(A)Cp^(B)MX_(n)  (I)

The metal atom “M” of the metallocene catalyst compound, as describedthroughout the specification and claims, may be selected from the groupconsisting of Groups 3 through 12 atoms and lanthanide Group atoms inone embodiment; and selected from the group consisting of Groups 3through 10 atoms in a more particular embodiment, and selected from thegroup consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co,Rh, Ir, and Ni in yet a more particular embodiment; and selected fromthe group consisting of Groups 4, 5 and 6 atoms in yet a more particularembodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment,and Zr in yet a more particular embodiment. The oxidation state of themetal atom “M” may range from 0 to +7 in one embodiment; and in a moreparticular embodiment, is +1, +2, +3, +4 or +5; and in yet a moreparticular embodiment is +2, +3 or +4. The groups bound the metal atom“M” is such that the compounds described below in the formulas andstructures are neutral, unless otherwise indicated. The Cp ligand(s)form at least one chemical bond with the metal atom M to form the“metallocene catalyst compound”. The Cp ligands are distinct from theleaving groups bound to the catalyst compound in that they are nothighly susceptible to substitution/abstraction reactions.

M is as described above; each X is chemically bonded to M; each Cp groupis chemically bonded to M; and n is 0 or an integer from 1 to 4, andeither 1 or 2 in a particular embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (I) may be thesame or different cyclopentadienyl ligands or ligands isolobal tocyclopentadienyl, either or both of which may contain heteroatoms andeither or both of which may be substituted by a group R. In oneembodiment, Cp^(A) and Cp^(B) are independently selected from the groupconsisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (I) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (I) include hydrogen radicals, hydrocarbyls, lowerhydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls,lower alkyls, substituted alkyls, heteroalkyls, alkenyls, loweralkenyls, substituted alkenyls, heteroalkenyls, alkynyls, loweralkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys,aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys,aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls,alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls,heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups,silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls,acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys,acylaminos, aroylaminos, and combinations thereof.

More particular non-limiting examples of alkyl substituents R associatedwith formula (I) includes methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, andtert-butylphenyl groups and the like, including all their isomers, forexample tertiary-butyl, isopropyl, and the like. Other possible radicalsinclude substituted alkyls and aryls such as, for example, fluoromethyl,fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl andhydrocarbyl substituted organometalloid radicals includingtrimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted Group 15 radicalsincluding dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents Rinclude olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example 3-butenyl,2-propenyl, 5-hexenyl and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron and combinations thereof. Also, a substituent group Rgroup such as 1-butanyl may form a bonding association to the element M.

Each X in formula (I) is independently selected from the groupconsisting of: any leaving group in one embodiment; halogen ions,hydrides, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls,heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls,heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls,heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls,heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios,lower alkyls thios, arylthios, thioxys, aryls, substituted aryls,heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides,haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles,heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos,phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos, and combinations thereof. In another embodiment, X is C₁ toC₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls,C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ toC₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂heteroatom-containing hydrocarbons and substituted derivatives thereofin a more particular embodiment; hydride, halogen ions, C₁ to C₆ alkyls,C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ alkoxys, C₆ to C₁₄aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆ alkylcarboxylates, C₁ to C₆fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls,and C₇ to C₁₈ fluoroalkylaryls in yet a more particular embodiment;hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl,fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀alkylaryls, substituted C₁ to C₁₂ alkyls, substituted C₆ to C₁₂ aryls,substituted C₇ to C₂₀ alkylaryls and C₁ to C₁₂ heteroatom-containingalkyls, C₁ to C₁₂ heteroatom-containing aryls and C₁ to C₁₂heteroatom-containing alkylaryls in yet a more particular embodiment;chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈alkylaryls, halogenated C₁ to C₆ alkyls, halogenated C₂ to C₆ alkenyls,and halogenated C₇ to C₁₈ alkylaryls in yet a more particularembodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl,dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- andtrifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- andpentafluorophenyls) in yet a more particular embodiment.

Other non-limiting examples of X groups in formula (I) include amines,phosphines, ethers, carboxylates, dienes, hydrocarbon radicals havingfrom 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., —C₆F₅(pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻),hydrides and halogen ions and combinations thereof. Other examples of Xligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl,heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene,methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),dimethylamide, dimethylphosphide radicals and the like. In oneembodiment, two or more X's form a part of a fused ring or ring system.

In another aspect, the metallocene catalyst component includes those offormula (I) where Cp^(A) and Cp^(B) are bridged to each other by atleast one bridging group, (A), such that the structure is represented byformula (II):Cp^(A)(A)Cp^(B)MX_(n)  (II)

These bridged compounds represented by formula (II) are known as“bridged metallocenes”. Cp^(A), Cp^(B), M, X and n are as defined abovefor formula (I); and wherein each Cp ligand is chemically bonded to M,and (A) is chemically bonded to each Cp. Non-limiting examples ofbridging group (A) include divalent alkyls, divalent lower alkyls,divalent substituted alkyls, divalent heteroalkyls, divalent alkenyls,divalent lower alkenyls, divalent substituted alkenyls, divalentheteroalkenyls, divalent alkynyls, divalent lower alkynyls, divalentsubstituted alkynyls, divalent heteroalkynyls, divalent alkoxys,divalent lower alkoxys, divalent aryloxys, divalent alkylthios, divalentlower alkyl thios, divalent arylthios, divalent aryls, divalentsubstituted aryls, divalent heteroaryls, divalent aralkyls, divalentaralkylenes, divalent alkaryls, divalent alkarylenes, divalenthaloalkyls, divalent haloalkenyls, divalent haloalkynyls, divalentheteroalkyls, divalent heterocycles, divalent heteroaryls, divalentheteroatom-containing groups, divalent hydrocarbyls, divalent lowerhydrocarbyls, divalent substituted hydrocarbyls, divalentheterohydrocarbyls, divalent silyls, divalent boryls, divalentphosphinos, divalent phosphines, divalent aminos, divalent amines,divalent ethers, divalent thioethers. Additional non-limiting examplesof bridging group A include divalent hydrocarbon groups containing atleast one Group 13 to 16 atom, such as but not limited to at least oneof a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium andtin atom and combinations thereof; wherein the heteroatom may also be C₁to C₁₂ alkyl or aryl substituted to satisfy neutral valency. Thebridging group (A) may also contain substituent groups R as definedabove for formula (I) including halogen radicals and iron. Moreparticular non-limiting examples of bridging group (A) are representedby C₁ to C₆ alkylenes, substituted C₁ to C₆ alkylenes, oxygen, sulfur,R′₂C═, R′₂Si═, —Si(R′)₂Si(R′₂)—, R′₂Ge═, R′P═ (wherein “═” representstwo chemical bonds), where R′ is independently selected from the groupconsisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted Group 15 atoms, substituted Group 16 atoms, and halogenradical; and wherein two or more R′ may be joined to form a ring or ringsystem. In one embodiment, the bridged metallocene catalyst component offormula (II) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene,ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene,1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene,dimethylsilyl, diethylsilyl, methyl-ethylsilyl,trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl,di(n-propyl)silyl, di(1-propyl)silyl, di(n-hexyl)silyl,dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl,t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and thecorresponding moieties wherein the Si atom is replaced by a Ge or a Catom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another embodiment, bridging group (A) may also be cyclic,comprising, for example 4 to 10, 5 to 7 ring members in a moreparticular embodiment. The ring members may be selected from theelements mentioned above, from one or more of B, C, Si, Ge, N and O in aparticular embodiment. Non-limiting examples of ring structures whichmay be present as or part of the bridging moiety are cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene andthe corresponding rings where one or two carbon atoms are replaced by atleast one of Si, Ge, N and O, in particular, Si and Ge. The bondingarrangement between the ring and the Cp groups may be either cis-,trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/orcarry one or more substituents and/or be fused to one or more other ringstructures. If present, the one or more substituents are selected fromthe group consisting of hydrocarbyl (e.g., alkyl such as methyl) andhalogen (e.g., F, Cl) in one embodiment. The one or more Cp groups whichthe above cyclic bridging moieties may optionally be fused to may besaturated or unsaturated and are selected from the group consisting ofthose having 4 to 10, more particularly 5, 6 or 7 ring members (selectedfrom the group consisting of C, N, O and S in a particular embodiment)such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover,these ring structures may themselves be fused such as, for example, inthe case of a naphthyl group. Moreover, these (optionally fused) ringstructures may carry one or more substituents. Illustrative,non-limiting examples of these substituents are hydrocarbyl(particularly alkyl) groups and halogen atoms.

The ligands Cp^(A) and Cp^(B) of formula (I) and (II) are different fromeach other in one embodiment, and the same in another embodiment.

In yet another aspect, the metallocene catalyst components includemono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalystcomponents) such as described in WO 93/08221 for example. In thisembodiment, the at least one metallocene catalyst component is a bridged“half-sandwich” metallocene represented by the formula (III):Cp^(A)(A)QMX_(n)  (III)wherein Cp^(A) is defined above and is bound to M; (A) is defined aboveand is a bridging group bonded to Q and Cp^(A); and wherein an atom fromthe Q group is bonded to M; and n is 0 or an integer from 1 to 3; 1 or 2in a particular embodiment. In formula (III), Cp^(A), (A) and Q may forma fused ring system. The X groups and n of formula (III) are as definedabove in formula (I) and (II). In one embodiment, Cp^(A) is selectedfrom the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, substituted versions thereof, andcombinations thereof.

In formula (III), Q is a heteroatom-containing ligand in which thebonding atom (the atom that is bonded with the metal M) is selected fromthe group consisting of Group 15 atoms and Group 16 atoms in oneembodiment, and selected from the group consisting of nitrogen,phosphorus, oxygen or sulfur atom in a more particular embodiment, andnitrogen and oxygen in yet a more particular embodiment. Non-limitingexamples of Q groups include ethers, amines, phosphines, thioethers,alkylamines, arylamines, mercapto compounds, ethoxy compounds,carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene,phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzeneother compounds comprising Group 15 and Group 16 atoms capable ofbonding with M.

In yet another aspect, the at least one metallocene catalyst componentis an unbridged “half sandwich” metallocene represented by the formula(IV):Cp^(A)MQ_(q)X_(n)  (IV)wherein Cp^(A) is defined as for the Cp groups in (I) and is a ligandthat is bonded to M; each Q is independently bonded to M; Q is alsobound to Cp^(A) in one embodiment; X is a leaving group as describedabove in (I); n ranges from 0 to 3, and is 1 or 2 in one embodiment; qranges from 0 to 3, and is 1 or 2 in one embodiment. In one embodiment,Cp^(A) is selected from the group consisting of cyclopentadienyl,indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, andcombinations thereof.

In formula (IV), Q is selected from the group consisting of ROO⁻, RO—,R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, andsubstituted and unsubstituted aryl groups, wherein R is selected fromthe group consisting of hydrocarbyls, lower hydrocarbyls, substitutedhydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substitutedalkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls,heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls,heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios,lower alkyls thios, arylthios, thioxys, aryls, substituted aryls,heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides,haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles,heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos,phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos, and combinations thereof. In another embodiment, R isselected from C₁ to C₆ alkyls, C₆ to C₁₂ aryls, C₁ to C₆ alkylamines, C₆to C₁₂ alkylarylamines, C₁ to C₆ alkoxys, C₆ to C₁₂ aryloxys, and thelike. Non-limiting examples of Q include C₁ to C₁₂ carbamates, C₁ to C₁₂carboxylates (e.g., pivalate), C₂ to C₂₀ alkyls, and C₂ to C₂₀heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can bedescribed as in formula (II), such as described in, for example, U.S.Pat. No. 6,069,213:Cp^(A)M(Q₂GZ)X_(n) or T(Cp^(A)M(Q₂GZ)X_(n))_(m)  (V)wherein M, Cp^(A), X and n are as defined above;

Q₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at leastone of the Q groups form a bond with M, and is defined such that each Qis independently selected from the group consisting of —O—, —NR—, —CR₂—and —S—; G is either carbon or silicon; and Z is selected from the groupconsisting of R, —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, and hydride,providing that when Q is —NR—, then Z is selected from the groupconsisting of —OR, —NR₂, —SR, —SiR₃, —PR₂; and provided that neutralvalency for Q is satisfied by Z; and wherein each R is independentlyselected from the group consisting of hydrocarbyls, lower hydrocarbyls,substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls,substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substitutedalkenyls, heteroalkenyls, alkynyls, lower alkynyls, substitutedalkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls,alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substitutedaryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes,halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls,heterocycles, heteroaryls, heteroatom-containing groups, silyls, boryls,phosphinos, phosphines, aminos, amines, cycloalkyls, acyls, aroyls,alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys,acylaminos, aroylaminos, and combinations thereof. In anotherembodiment, R is selected from the group consisting of C₁ to C₁₀heteroatom containing groups, C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ toC₁₂ alkylaryls, C₁ to C₁₀ alkoxys, and C₆ to C₁₂ aryloxys;

n is 1 or 2 in a particular embodiment; and

T is a bridging group selected from the group consisting of C₁ to C₁₀alkylenes, C₆ to C₁₂ arylenes and C₁ to C₁₀ heteroatom containinggroups, and C₆ to C₁₂ heterocyclic groups; wherein each T group bridgesadjacent “Cp^(A)M(Q₂GZ)X_(n)” groups, and is chemically bonded to theCp^(A) groups.

m is an integer from 1 to 7; m is an integer from 2 to 6 in a moreparticular embodiment.

In another aspect, the at least one metallocene catalyst component canbe described more particularly in structures (VIa), (VIb), (VIc), (VId),(VIe), and (VIf):

wherein in structures (VIa) to (VIf), M is selected from the groupconsisting of Group 3 to Group 12 atoms, and selected from the groupconsisting of Group 3 to Group 10 atoms in a more particular embodiment,and selected from the group consisting of Group 3 to Group 6 atoms inyet a more particular embodiment, and selected from the group consistingof Group 4 atoms in yet a more particular embodiment, and selected fromthe group consisting of Zr and Hf in yet a more particular embodiment;and is Zr in yet a more particular embodiment;

wherein Q in (VIa) to (VIf) is selected from the group consisting ofhydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls,heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls,heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls,heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls,heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios,lower alkyls thios, arylthios, thioxys, aryls, substituted aryls,heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides,haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles,heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos,phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos, alkylenes, aryls, arylenes, alkoxys, aryloxys, amines,arylamines (e.g., pyridyl) alkylamines, phosphines, alkylphosphines,substituted alkyls, substituted aryls, substituted alkoxys, substitutedaryloxys, substituted amines, substituted alkylamines, substitutedphosphines, substituted alkylphosphines, carbamates, heteroallyls,carboxylates (non-limiting examples of suitable carbamates andcarboxylates include trimethylacetate, trimethylacetate, methylacetate,p-toluate, benzoate, diethylcarbamate, and dimethylcarbamate),fluorinated alkyls, fluorinated aryls, and fluorinatedalkylcarboxylates; wherein the saturated groups defining Q comprise from1 to 20 carbon atoms in one embodiment; and wherein the aromatic groupscomprise from 5 to 20 carbon atoms in one embodiment; wherein R* may beselected from divalent alkyls, divalent lower alkyls, divalentsubstituted alkyls, divalent heteroalkyls, divalent alkenyls, divalentlower alkenyls, divalent substituted alkenyls, divalent heteroalkenyls,divalent alkynyls, divalent lower alkynyls, divalent substitutedalkynyls, divalent heteroalkynyls, divalent alkoxys, divalent loweralkoxys, divalent aryloxys, divalent alkylthios, divalent lower alkylthios, divalent arylthios, divalent aryls, divalent substituted aryls,divalent heteroaryls, divalent aralkyls, divalent aralkylenes, divalentalkaryls, divalent alkarylenes, divalent haloalkyls, divalenthaloalkenyls, divalent haloalkynyls, divalent heteroalkyls, divalentheterocycles, divalent heteroaryls, divalent heteroatom-containinggroups, divalent hydrocarbyls, divalent lower hydrocarbyls, divalentsubstituted hydrocarbyls, divalent heterohydrocarbyls, divalent silyls,divalent boryls, divalent phosphinos, divalent phosphines, divalentaminos, divalent amines, divalent ethers, divalent thioethers.Additionally, R* may be from the group of divalent hydrocarbylenes andheteroatom-containing hydrocarbylenes in one embodiment; and selectedfrom the group consisting of alkylenes, substituted alkylenes andheteroatom-containing hydrocarbylenes in another embodiment; andselected from the group consisting of C₁ to C₁₂ alkylenes, C₁ to C₁₂substituted alkylenes, and C₁ to C₁₂ heteroatom-containinghydrocarbylenes in a more particular embodiment; and selected from thegroup consisting of C₁ to C₄ alkylenes in yet a more particularembodiment; and wherein both R* groups are identical in anotherembodiment in structures (VIf);

A is as described above for (A) in structure (II), and moreparticularly, selected from the group consisting of a chemical bond,—O—, —S—, —SO₂—, —NR—, ═SiR₂, =GeR₂, ═SnR₂, —R₂SiSiR₂—, RP═, C₁ to C₁₂alkylenes, substituted C₁ to C₁₂ alkylenes, divalent C₄ to C₁₂ cyclichydrocarbons and substituted and unsubstituted aryl groups in oneembodiment; and selected from the group consisting of C₅ to C₈ cyclichydrocarbons, —CH₂CH₂—, ═CR₂ and ═SiR₂ in a more particular embodiment;wherein and R is selected from the group consisting of alkyls,cycloalkyls, aryls, alkoxys, fluoroalkyls and heteroatom-containinghydrocarbons in one embodiment; and R is selected from the groupconsisting of C₁ to C₆ alkyls, substituted phenyls, phenyl, and C₁ to C₆alkoxys in a more particular embodiment; and R is selected from thegroup consisting of methoxy, methyl, phenoxy, and phenyl in yet a moreparticular embodiment; wherein A may be absent in yet anotherembodiment, in which case each R* is defined as for R¹-R¹³; each X is asdescribed above in (I); n is an integer from 0 to 4, and from 1 to 3 inanother embodiment, and 1 or 2 in yet another embodiment; and R¹ throughR¹³ are independently: selected from the group consisting of hydrogenradicals, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls,heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls,heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls,heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls,heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios,lower alkyls thios, arylthios, thioxys, aryls, substituted aryls,heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides,haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles,heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos,phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos through R¹³ may also be selected independently from C₁ toC₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls,C₁ to C₁₂ alkoxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁to C₁₂ heteroatom-containing hydrocarbons and substituted derivativesthereof in one embodiment; selected from the group consisting ofhydrogen radical, fluorine radical, chlorine radical, bromine radical,C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆fluoroalkyls, C₂ to C₆ fluoroalkenyls, C₇ to C₁₈ fluoroalkylaryls in amore particular embodiment; and hydrogen radical, fluorine radical,chlorine radical, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tertiary butyl, hexyl, phenyl, 2,6-di-methylpheyl, and4-tertiarybutylpheyl groups in yet a more particular embodiment; whereinadjacent R groups may form a ring, either saturated, partiallysaturated, or completely saturated.

The structure of the metallocene catalyst component represented by (XIa)may take on many forms such as disclosed in, for example, U.S. Pat. No.5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No. 5,747,406,including a dimmer or oligomeric structure, such as disclosed in, forexample, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213.

In a particular embodiment of the metallocene represented in (VId), R¹and R² form a conjugated 6-membered carbon ring system that may or maynot be substituted.

In one non-limiting embodiment, the metallocene compound is selectedfrom the group consisting of(Pentamethylcyclopentadienyl)(Propylcyclopentadienyl)ZrX′₂,(Tetramethylcyclopentadienyl)(Propylcyclopentadienyl)ZrX′₂,(Pentamethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX′₂,(Tetramethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX′₂,Me2Si(Indenyl)2ZrX2, Me2Si(Tetrahydroindenyl)2ZrX′₂, (n-propylcyclopentadienyl)2ZrX′₂, (n-propyl cyclopentadienyl)2HfX′₂, (n-butylcyclopentadienyl)2ZrX′₂, (n-butyl cyclopentadienyl)2HfX′₂, (1-Methyl,3-Butyl cyclopentadienyl)2ZrX′₂, HN(CH2CH2N(2,4,6-Me3-Phenyl))2ZrX′₂,HN(CH2CH2N(2,3,4,5,6-Me5-Phenyl))2ZrX′2, (1-Me, 3-Bu-Cp)2ZrCl2,(CpPr)(Me4 Cp)HfCl2, (CpBu)2ZrCl2, (CpPr)2ZrCl2, (CpBu)2HfCl2,(CpPr)2HfCl2, and any combinations thereof.

By “derivatives thereof”, it is meant any substitution or ring formationas described above; and in particular, replacement of the metal “M” (Cr,Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr,Hf and Ti; and replacement of the “X” group with any of C₁ to C₅ alkyls,C₆ aryls, C₆ to C₁₀ alkylaryls, fluorine or chlorine; n is 1, 2 or 3.

It is contemplated that the metallocene catalysts components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

As used herein, a single, bridged, asymmetrically substitutedmetallocene catalyst component having a racemic and/or meso isomer doesnot, itself, constitute at least two different bridged, metallocenecatalyst components.

The “metallocene catalyst component” may comprise any combination of any“embodiment” described herein.

Metallocene compounds and catalysts are known in the art and any one ormore may be utilized herein. Suitable metallocenes include but are notlimited to all of the metallocenes disclosed and referenced in the U.S.patents cited above, as well as those disclosed and referenced in U.S.Pat. Nos. 7,179,876, 7,169,864, 7,157,531, 7,129,302, 6,995,109,6,958,306, 6,884748, 6,689,847, U.S. Patent Application publicationnumber 2007/0055028, and published PCT Application Nos. WO 97/22635, WO00/699/22, WO 01/30860, WO 01/30861, WO 02/46246, WO 02/50088, WO04/026921, and WO 06/019494, all fully incorporated herein by reference.Additional catalysts suitable for use herein include those referenced inU.S. Pat. Nos. 6,309,997, 6,265,338, U.S. Patent Application publicationnumber 2006/019925, and the following articles: Chem Rev 2000, 100,1253, Resconi; Chem Rev 2003, 103, 283; Chem. Eur. J. 2006, 12, 7546Mitsui; J Mol Catal A 2004, 213, 141; Macromol Chem Phys, 2005, 206,1847; and J Am Chem Soc 2001, 123, 6847.

Group 15-Containing Catalysts

“Group 15-containing catalyst components”, as referred to herein,include Group 3 to Group 12 metal complexes, wherein the metal is 2 to 4coordinate, the coordinating moiety or moieties including at least twoGroup 15 atoms, and up to four Group 15 atoms. In one embodiment, theGroup 15-containing catalyst component is a complex of a Group 4 metaland from one to four ligands such that the Group 4 metal is at least 2coordinate, the coordinating moiety or moieties including at least twonitrogens. Representative Group 15-containing compounds are disclosedin, for example, WO 98/46651, WO 99/01460; EP A1 0 893,454; EP A1 0 894005; U.S. Pat. No. 5,318,935; U.S. Pat. No. 5,889,128 U.S. Pat. No.6,333,389 B2 and U.S. Pat. No. 6,271,325 B1.

The Group 15-containing catalyst components are prepared by methodsknown in the art, such as those disclosed in, for example, EP 0 893 454A1, U.S. Pat. No. 5,889,128, U.S. Pat. No. 6,333,389 B2 and WO 00/37511.

The “Group 15-containing catalyst component” may comprise anycombination of any “embodiment” described herein.

Phenoxide Transition Metal Catalysts

Phenoxide transition metal catalyst compositions are heteroatomsubstituted phenoxide ligated Group 3 to 10 transition metal orlanthanide metal compounds wherein the metal is bound to the oxygen ofthe phenoxide group. Phenoxide transition metal catalyst compounds maybe represented by Formula XIV or XV:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiaryalkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may ormay not also be bound to M;

at least one of R² to R⁵ is a heteroatom containing group, the rest ofR² to R⁵ are independently hydrogen or a C₁ to C₁₀₀ group, preferably aC₄ to C₂₀ alkyl group, preferred examples of which include butyl,isobutyl, t-butyl, pentyl, hexyl, heptyl, isohexyl, octyl, isooctyl,decyl, nonyl, dodecyl, and any of R² to R⁵ also may or may not be boundto M;

Each R¹ to R⁵ group may be independently substituted or unsubstitutedwith other atoms, including heteroatoms or heteroatom containinggroup(s);

O is oxygen;

M is a Group 3 to Group 10 transition metal or lanthanide metal,preferably a Group 4 metal, preferably M is Ti, Zr or Hf;

n is the valence state of the metal M, preferably 2, 3, 4, or 5; and

Q is, and each Q may be independently be, an alkyl, halogen, benzyl,amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, or abond to an R group containing a heteroatom which may be any of R¹ to R⁵.

A heteroatom containing group may be any heteroatom or a heteroatombound to carbon, silicon or another heteroatom. Preferred heteroatomsinclude boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin,lead, antimony, oxygen, selenium, and tellurium. Particularly preferredheteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even moreparticularly preferred heteroatoms include nitrogen and oxygen. Theheteroatom itself may be directly bound to the phenoxide ring or it maybe bound to another atom or atoms that are bound to the phenoxide ring.The heteroatom containing group may contain one or more of the same ordifferent heteroatoms. Preferred heteroatom containing groups includeimines, amines, oxides, phosphines, ethers, ketones, oxoazolinesheterocyclics, oxazolines, thioethers, and the like.

Particularly preferred heteroatom containing groups include imines. Anytwo adjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

In a preferred embodiment the heteroatom substituted phenoxidetransition metal compound is an iminophenoxide Group 4 transition metalcompound, and more preferably an iminophenoxidezirconium compound.

It is further contemplated by the invention that other catalysts can becombined with the compounds of the invention. For example, see Hlalky,G. G. Chem. Rev. (2000), 100, 1347; Alt, H.; Koppl, A. Chem. Rev.(2000), 100, 1205; Resconi, L. et al., Chem. Rev. (2000), 100, 1253;Bryntzinger, H. H. et. al., Angew. Chem. Int. Ed. Engl. (1995), 34,1143; Ittel, S. D. et al., Chem. Rev. (2000), 100, 1169; Gibson, V. C.et al., Chem. Rev. (2003), 103, 283; Skupinska, J., Chem. Rev. (1991),91, 613; Carter, A. et al., Chem. Commun., 2002, 858; McGuinness, D. S.;et al., J. Am. Chem. Soc. (2003), 125, 5272; McGuiness, D. S., Chem.Commun (2003), 334; U.S. Pat. Nos. 4,937,299, 4,935,474, 5,281,679,5,359,015, 5,470,811, and 5,719,241, all of which are herein fullyincorporated herein reference.

In another embodiment of the invention one or more catalyst compounds orcatalyst systems may be used in combination with one or moreconventional-type catalyst compounds or catalyst systems. Non-limitingexamples of mixed catalysts and catalyst systems are described in U.S.Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255,5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031, andPCT Publication No. WO 96/23010 published Aug. 1, 1996, all of which areherein fully incorporated by reference.

High Molecular Weight Catalysts

With respect to the catalyst systems of the disclosure wherein the highmolecular weight catalyst compound is a non-metallocene compoundgenerally the compound is a biphenyl phenol catalyst (BPP) compound. BPPcatalyst compounds are known in the art and any are suitable for useherein such as, but not limited to those disclosed in U.S. Pat. Nos.7,091,282, 7,030,256, 7,060,848, 7,126,031, 6,841,502, U.S. PatentApplication publication numbers 2006/0025548, 2006/020588,2006/00211892, and published PCT application numbers WO 2006/020624, WO2005/108406, and WO 2003/091262, all incorporated herein by reference.

Preference may be given to BPP compounds having formula (XVI) shownbelow:

wherein M may be Ti, Zr, or HE In one embodiment R¹ of formula I ishydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl,alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl,lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy,aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl,substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene,halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle,heteroaryl, heteroatom-containing group, silyl, boryl, phosphino,phosphine, amino, amine

In some embodiments, the bridging group R¹ is selected from the groupconsisting of optionally substituted divalent hydrocarbyl and divalentheteroatom containing hydrocarbyl. In other embodiments, R¹ is selectedfrom the group consisting of optionally substituted divalent alkyl,divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl,divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl,divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl,divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy,divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalentlower alkyl thio, divalent arylthio, divalent aryl, divalent substitutedaryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene,divalent alkaryl, divalent alkarylene, divalent halide, divalenthaloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalentheteroalkyl, divalent heterocycle, divalent heteroaryl, divalentheteroatom-containing group, divalent hydrocarbyl, divalent lowerhydrocarbyl, divalent substituted hydrocarbyl, divalentheterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino,divalent phosphine, divalent amino, divalent amine, divalent ether,divalent thioether. In still other embodiments, R¹ can be represented bythe general formula -(Q″R⁴⁰ _(2-z)″)_(z′)— wherein each Q″ is eithercarbon or silicon and each R⁴⁰ may be the same or different from theothers such that each R⁴⁰ is selected from the group consisting ofhydride and optionally substituted hydrocarbyl, and optionally two ormore R⁴⁰ groups may be joined into a ring structure having from 3 to 50atoms in the ring structure (not counting hydrogen atoms); and z′ is aninteger from 1 to 10, more specifically from 15 and even morespecifically from 25 and z″ is 0, 1 or 2. For example, when z″ is 2,there is no R⁴⁰ groups associated with Q″, which allows for those caseswhere one Q″ is multiply bonded to a second Q″. In more specificembodiments, R⁴⁰ is selected from the group consisting of hydride,halide, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thioxy, alkylthio, arylthio, andcombinations thereof. Specific R¹ groups within these embodimentsinclude —(CH₂)₂—, —(CH₂)₄— and —(CH₂)—(C₆H₄)—(CH₂)—. Other specificbridging moieties are set forth in the example ligands and complexesherein.

In one embodiment R²-R⁹ of formula (XVI) are optionally hydrocarbyl,lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl,lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl,substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substitutedalkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl,alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl,heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl,haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl,heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino,or amine

Each X in formula (XVI) is independently selected from the groupconsisting of: any leaving group in one embodiment; halogen ions,hydrides, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ toC₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈alkylaryloxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ toC₁₂ heteroatom-containing hydrocarbons and substituted derivativesthereof in a more particular embodiment; hydride, halogen ions, C₁ to C₆alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ alkoxys, C₆ toC₁₄ aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆ alkylcarboxylates, C₁ toC₆ fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls,and C₇ to C₁₈ fluoroalkylaryls in yet a more particular embodiment;hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl,fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀alkylaryls, substituted C₁ to C₁₂ alkyls, substituted C₆ to C₁₂ aryls,substituted C₇ to C₂₀ alkylaryls and C₁ to C₁₂ heteroatom-containingalkyls, C₁ to C₁₂ heteroatom-containing aryls and C₁ to C₁₂heteroatom-containing alkylaryls in yet a more particular embodiment;chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈alkylaryls, halogenated C₁ to C₆ alkyls, halogenated C₂ to C₆ alkenyls,and halogenated C₇ to C₁₈ alkylaryls in yet a more particularembodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl,dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- andtrifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- andpentafluorophenyls) in yet a more particular embodiment.

Other non-limiting examples of X groups in formula (XVI) include amines,phosphines, ethers, carboxylates, dienes, hydrocarbon radicals havingfrom 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., —C₆F₅(pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻),hydrides and halogen ions and combinations thereof. Other examples of Xligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl,heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene,methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),dimethylamide, dimethylphosphide radicals and the like. In oneembodiment, two or more X's form a part of a fused ring or ring system.

In one embodiment of the compound represented by formula (XVI), M may beTi, Zr, or Hf. R¹, R³, R⁵ through R⁹ are H; each R² may be any of alkyl,aryl, or heteroaryl; each R⁴ may be any of H, alkyl, aryl; and each Xmay be any of F, Cl, Br, I, Me, Bnz, CH₂SiMe₃, or C1 to C5 alkyls.

In another non-limiting embodiment of the compound represented byformula (XVI), M may be Ti, Zr, or Hf; R¹ may be any of CH₂CH₂, (CH₂)₃,(CH₂)₄, CH₂CHMeCH₂, CH₂CMe₂CH₂, Me₂S₁, CH₂SiMe₂CH₂, each R² may be anyof an aryl group, defined here to bind through the 1-position to the BPPring, with substituents in the 2-position or substituents in the 2 and 6positions such as 2,4-Me₂Ph, 2,5-Me₂Ph, 2,6-Me₂Ph, 2,6-Et₂Ph,2,6-Pr₂-Ph, 2,6-Bu₂Ph, 2-MeNapthyl, 2,4,6-Me₃Ph, 2,4,6-Et₃Ph,2,4,6-Pr₃Ph, carbazole and substituted carbazoles; R³ and R⁵ through R⁹are H; each R⁴ may be any of H, Methyl, Ethyl, Propyl, Butyl, Pentyl;and each X may be any of F, Cl, Br, I, Me, Bnz, CH₂SiMe₃, or C1 to C5alkyls.

In one preferred embodiment, M may be either Zr or Hf; and X may be anyof F, Cl, Br, I, Me, Bnz, or CH₂SiMe₃. In another preferred embodiment,M may be either Zr or Hf; R¹ may be either (CH₂)₃ or (CH₂)₄; each R² maybe any of 2,6-Me2Ph, 2,6-Et2Ph, 2,6-Pr2-Ph, 2,6-Bu2Ph, 2-MeNapthyl,2,4,6-Me3Ph, 2,4,6-Et3Ph, 2,4,6-Pr3Ph, and carbazole; each R⁴ may be anyof H, Methyl or Butyl; and X may be any of F, Cl, or Me. In even anotherpreferred embodiment, the R¹ is (CH₂)₃; each R³ is either 2,4,6-Me₃Ph or2-MeNapthyl; each R⁴ is CH₃; X is Cl; and M is Zr.

In another non-limiting embodiment, the high molecular weight catalystcomponent may be any catalyst that produces a polymer having a weightaverage molecular weight (Mw) of greater than about 1 million g/mol,preferably greater than about 1.5 million g/mol, even more preferablygreater than about 2 million g/mol, and still more preferably greaterthan about 3 million g/mol. The low molecular weight catalyst may be anycatalyst that produces a polymer having a weight average molecularweight (Mw) in the range of from about 40,000 to about 200,000 g/mol,preferably from about 50,000 to about 180,000 g/mol, more preferablyfrom about 60,000 to about 175,000 g/mol, and even more preferably fromabout 70,000 to about 150,000 g/mol. In one preferred embodiment, thehigh molecular weight catalyst produces polymer having an Mw greaterthan about 5 million g/mol, and the low molecular weight catalystproduces polymer having an Mw of about 100,000 g/mol.

The amount of each catalyst component present in the catalyst systems ofthe disclosure may be varied within a range. The amount of each catalystcomponent present in the catalyst systems may be dependent on one ormore reaction parameters including but not limited to reactortemperature, hydrogen concentration, and comonomer concentration. Thelow molecular weight catalyst is generally present in an amount greaterthan that of the high molecular weight catalyst. Generally, the highmolecular weight catalyst component is present in a catalyst system inan amount in a range of from about 0.001 to about 5.0 mol % of said lowmolecular weight catalyst component, preferably in a range of from about0.05 to about 2.5 mol % of said low molecular weight catalyst component,more preferably in a range of from about 0.1 to about 2.0 mol % of saidlow molecular weight catalyst component. For example, in the case of onehigh and one low molecular weight catalyst, the mol % of the highmolecular weight catalyst may be calculated from the equation: 100(moles of high molecular weight catalyst)/(moles of low molecular weightcatalyst+moles of high molecular weight catalyst).

Activators and Activation Methods

The above described low and high molecular weight precatalyst compoundscan be combined with an activator and optionally a support or carrier ina manner that will allow production of a polymer with low and highmolecular weight components. The term “cocatalyst” or “cocatalysts” maybe used interchangeably with one or more “activators”. This activationyields catalyst compounds capable of polymerizing olefins.

For the purposes of this patent specification and appended claims, theterm “activator” is defined to be any compound or component or methodwhich can activate any of the precatalyst metal compounds of theinvention as described above. Non-limiting activators, for example mayinclude a Lewis acid or a non-coordinating ionic activator or ionizingactivator or any other compound including Lewis bases, aluminum alkyls,conventional-type cocatalysts or an activator-support and combinationsthereof that can convert a neutral precatalyst metal compound to acatalytically active cationic metal compound. It is within the scope ofthis invention to use alumoxane or modified alumoxane as an activator,and/or to also use ionizing activators, neutral or ionic, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron or atrisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtylboron metalloid precursor that would ionize the neutral precatalystmetal compound.

The low and high molecular weight catalyst precursors according to thisinvention may be activated for polymerization catalysis in any mannersufficient to allow coordination or cationic polymerization. This can beachieved for coordination polymerization when one ligand can beabstracted and another will either allow insertion of the unsaturatedmonomers or will be similarly abstractable for replacement with a ligandthat allows insertion of the unsaturated monomer (labile ligands), eg.alkyl, silyl or hydride. The traditional activators of coordinationpolymerization art are suitable, those typically include Lewis acidssuch as alumoxane compounds, and ionizing, anion precursor compoundsthat abstract one so as to ionize the bridged metallocene metal centerin to a cation and provide a counterbalancing noncoordianting ion. Inone embodiment, an activation method using ionizing ionic compounds notcontaining an active proton but capable of producing both a cationicmetal compound catalyst and a non-coordinating anion are alsocontemplated, and are described in EP-A-0 426 637, EP-A-0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

Alkylalumoxanes and modified alkylalumoxane are suitable as catalystactivators, particularly for the invention metal compounds whereR¹=halide or other functional group. Alkylalumoxanes and modifiedalkylalumoxane are also suitable as catalyst for the invention metalcompounds where R¹=hydrocarbyl or substituted hydrocarbyl. In oneembodiment, one or more alumoxanes are utilized as an activator in thecatalyst composition of the invention. Alumoxanes, sometimes calledaluminoxanes in the art, are generally oligomeric compounds containing—Al(R)—O— subunits, where R is an alkyl group. Examples of alumoxanesinclude methylalumoxane (MAO), modified methylalumoxane (MMAO),ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modifiedalkylalumoxanes are suitable as catalyst activators, particularly whenthe abstractable ligand is a halide. Mixtures of different alumoxanesand modified alumoxanes may also be used. For further descriptions, seeU.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180.

Alumoxanes may be produced by the hydrolysis of the respectivetrialkylaluminum compound. MMAO may be produced by the hydrolysis oftrimethylaluminum and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in U.S. Pat. Nos. 4,665,208, 4,952,540,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463,4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451,5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and Europeanpublications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0586 665, and PCT publications WO 94/10180 and WO 99/15534, all of whichare herein fully incorporated by reference. It may be preferable to usea visually clear methylalumoxane. A cloudy or gelled alumoxane can befiltered to produce a clear solution or clear alumoxane can be decantedfrom the cloudy solution. Another preferred alumoxane is a modifiedmethyl alumoxane (MMAO) cocatalyst type 3A (commercially available fromAkzo Chemicals, Inc. under the trade name Modified Methylalumoxane type3A, covered under U.S. Pat. No. 5,041,584).

Aluminum alkyl or organoaluminum compounds which may be utilized asactivators (or scavengers) include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Suitable anions are known in the art and will be suitable for use withthe catalysts of the invention. See in particular, U.S. Pat. No.5,278,119, WO2002102857, WO2002051884, WO200218452, WO2000037513,WO2000029454, WO2000004058, WO9964476, WO2003049856, WO2003051892,WO2003040070, WO2003000740, WO2002036639, WO2002000738, WO2002000666,WO2001081435, WO2001042249, WO2000004059. Also see the review articlesby S. H. Strauss, “The Search for Larger and More Weakly CoordinatingAnions”, Chem. Rev., 93, 927-942 (1993) and C. A. Reed, “Carboranes: ANew Class of Weakly Coordinating Anions for Strong Electrophiles,Oxidants and Superacids”, Acc. Chem. Res., 31, 133-139 (1998).

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis(heptafluoronaphthyl)borate, triethylammoniumtetrakis(heptafluoronaphthyl)borate, tripropylammoniumtetrakis(heptafluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(heptafluoronaphthyl)borate, tri(sec-butyl)ammonium tetrakis(heptafluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(heptafluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(heptafluoronaphthyl)borate, trimethylammonium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate, triethylammonium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate, tripropylammonium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate,tri(n-butyl)ammonium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate,tri(sec-butyl)ammonium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate,N,N-dimethylanilinium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate,N,N-diethylanilinium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, andN,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and tri-substituted phosphonium saltssuch as: triphenylphosphonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;non-Bronsted acids such as triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(heptafluoronaphthyl)borate, triphenylcarbenium(2-perfluorobiphenyl)₃(perfluorophenylalkynyl)borate,trisperfluorophenyl borane, and triperfluoronaphthyl borane.

In general the combined activator and metal compounds are combined inratios of about 1000:1 to about 0.5:1.

When the activator is an alumoxane (modified or unmodified), anyquantity of alumoxane that activates a precatalyst metal compound may beused. Preferably, the ratio of Aluminum to the total molar amount ofprecatalyst or catalyst metal is between 1000:1 and 1:1. Morepreferably, the ratio is from 500:1 to 25:1. Even more preferably, theratio is from 250:1 to 50:1. Even more preferably, the ratio is between200:1 and 75:1.

When the activator is an ionizing activator, any quantity of ionizingactivator that activates a precatalyst metal compound may be used.Preferably, the ratio of ionizing activator to the total molar amount ofprecatalyst or catalyst metal is between 10:1 and 1:10. More preferably,the ratio is from 5:1 to 1:5. Even more preferably, the ratio is from4:1 to 1:4. Even more preferably, the ratio is between 2:1 and 1:2.

When a combination of activators is employed, any quantity of activatorsthat activates precatalyst metal compounds may be used.

Supports and Methods of Supporting

In a preferred embodiment, the catalysts of the invention comprise highand low molecular weight catalyst precursors, an activator and a supportmaterial. Methods for preparing supported catalysts are well known inthe art and are easily extendible to the preparation of catalysts withhigh and low molecular weight catalyst metal compounds.

The above described precatalyst metal compounds and activators may becombined with one or more support materials or carriers using one of thesupport methods well known in the art or as described below. In thepreferred embodiment, the method of the invention uses a polymerizationcatalyst in a supported form. For example, in a most preferredembodiment, a catalyst system is in a supported form, for exampledeposited on, bonded to, contacted with, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

The terms “support” or “carrier” are used interchangeably and are anysupport material, preferably a porous support material, for example,talc, inorganic oxides and inorganic chlorides. Other carriers includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene divinyl benzenepolyolefins or polymeric compounds, zeolites, clays, or any otherorganic or inorganic support material and the like, or mixtures thereof.

The preferred carriers are inorganic oxides that include those Group 2,3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica,alumina, silica-alumina, magnesium chloride, and mixtures thereof. Otheruseful supports include magnesia, titania, zirconia, montmorillonite(EP-B1 0 511 665) and the like. Also, combinations of these supportmaterials may be used, for example, silica-chromium, silica-alumina,silica-titania and the like.

It is preferred that the carrier, most preferably an inorganic oxide,has a surface area in the range of from about 10 to about 700 m²/g, porevolume in the range of from about 0.1 to about 4.0 mL/g and averageparticle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5mL/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 mL/g andaverage particle size is from about 5 to about 100 The average pore sizeof the carrier of the invention typically has pore size in the range offrom 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75to about 350 Å.

Examples of supporting catalyst systems are described in Hlalky, Chem.Rev. (2000), 100, 1347 1376 and Fink et al., Chem. Rev. (2000), 100,1377 1390, U.S. Pat. Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821,4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925,5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704,5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487,5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032 and5,770,664, U.S. application Ser. No. 271,598 filed Jul. 7, 1994 and Ser.No. 788,736 filed Jan. 23, 1997, and PCT Publication Nos. WO 95/32995,WO 95/14044, WO 96/06187 and WO 97/02297, all of which are herein fullyincorporated by reference.

In one embodiment, the catalyst compounds of the invention may bedeposited on the same or separate supports together with an activator,or the activator may be used in an unsupported form, or may be depositedon a support different from the supported catalyst metal compounds ofthe invention, or any combination thereof.

Polymerization Processes

The catalyst systems and polymerization processes of the presentdisclosure are directed to polymerization of one or more olefin monomershaving from 2 to 30 carbon atoms. The catalysts and polymerizationprocesses are particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 4-methyl-1-pentene,1-isobutene, 1-isobutene and 1-decene. Other monomers useful in theprocesses of the disclosure include ethylenically unsaturated monomers,diolefins having 4 to 18 carbon atoms, conjugated or nonconjugateddienes, polyenes, vinyl monomers and cyclic olefins. Non-limitingmonomers useful in the disclosure may include norbornene, norbornadiene,isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkylsubstituted styrene, ethylidene norbornene, dicyclopentadiene andcyclopentene.

The present disclosure encompasses homopolymerization processescomprising a single olefin species such as ethylene or propylene, aswell as copolymerization reactions between one olefin species (referredto herein as the “monomer” and “monomer compound”) and at least a secondolefin species (referred to herein as “comonomer” and “comonomercompound”) different from the first species. Generally a copolymer willcomprise a major amount of the monomer compound (i.e., greater thanabout 50 mole percent) and a minor amount of the comonomer (i.e., lessthan about 50 mole percent). The comonomers generally have from three toabout 20 carbon atoms in their molecular chain and examples include, butare not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene,1-heptene, 2-heptene, 3-heptene, the four normal octenes, the fournormal nonenes, or the five normal decenes. In one non-limitingembodiment, a copolymer may comprise ethylene copolymerized with acomonomer selected from 1-butene, 1-pentene, 1-hexene, 1-octene,1-decene, or styrene.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer. In oneembodiment, two of the three monomers of the terpolymer are butene andethylene. In one embodiment, the comonomer content is 1.0 to 20.0 wt %,or 2.0 to 15.0 wt %.

The polymerization processes of the present disclosure may be utilizedfor production of any polyolefin though preference is given tohomopolymers and copolymers of polyethylene. In one non-limitingembodiment, the polyolefins are copolymers of ethylene and at least onecomonomer selected from the group consisting of propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, and combinations thereof. Inanother non-limiting embodiment, the polyolefins are bimodal copolymersof ethylene and at least one comonomer selected from the groupconsisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,1-octene, and combinations thereof.

Polymerization reactors suitable for the present disclosure may be anytype of reactor known in the art and may comprise at least one rawmaterial feed system, at least one feed system for catalyst or catalystcomponents, at least one reactor system, at least one polymer recoverysystem or any suitable combination thereof. Suitable reactors for thepresent disclosure may further comprise any one or more of any of acatalyst storage system, an extrusion system, a cooling system, adiluent recycling system, or a control system. Such reactors maycomprise continuous take-off and direct recycling of catalyst, diluent,and polymer. Generally, continuous processes may comprise the continuousintroduction of a monomer, a catalyst, and optionally a diluent into apolymerization reactor and the continuous removal from this reactor ofpolymer and recycling of diluent and unreacted monomers and comonomers.

The comonomer, if present in the polymerization reactor, is present atany level that will achieve the desired weight percent incorporation ofthe comonomer into the finished polyethylene. This is expressed as amole ratio of comonomer to ethylene as described herein, which is theratio of the gas concentration of comonomer moles in the cycle gas tothe gas concentration of ethylene moles in the cycle gas. In oneembodiment, the comonomer is present with ethylene in the cycle gas in amole ratio range of from 0 or 0.0001 (comonomer:ethylene) to 0.20 or0.10, and from 0.001 to 0.080 in another embodiment, and from 0.001 to0.050 in even another embodiment, and from 0.002 to 0.20 in stillanother embodiment. In yet another embodiment, the comonomer is presentwith ethylene in the cycle gas in a mole ratio range comprising anycombination of any upper limit with any lower limit as described herein.

The processes of the present disclosure may be characterized in that thedesired composition of high molecular weight to low molecular weightmoiety can be achieved at any of the above comonomer to ethylene ratios.

Hydrogen, if present in the polymerization reactor, is present at anylevel that will achieve the desired melt index (MI, or 12) and molecularweights of the high and the low molecular weight component. Using thecatalyst systems of the present disclosure increasing the concentrationof hydrogen may increase the melt index of the polyolefin generated. MIcan thus be influenced by the hydrogen concentration. The amount ofhydrogen in the polymerization can be expressed as a mole ratio relativeto the total polymerizable monomer, for example, ethylene, or a blend ofethylene and another alpha olefin. The amount of hydrogen used in thepolymerization processes of the present disclosure is an amountnecessary to achieve the desired MI of the final polyolefin resin.

In one embodiment, the ratio of hydrogen to total ethylene monomer (molppm H2:mol % ethylene) in the circulating gas stream is in a range offrom 0 to 100, in a range of from 0.05 to 50 in another embodiment, in arange of from 0.10 to 40 in even another embodiment, and in a range offrom 0.15 to 35 in still another embodiment. In yet another embodiment,the ratio of hydrogen to total ethylene monomer (mol ppm H2: mol %ethylene) in the circulating gas stream may be in a range comprising anycombination of any upper mole ratio limit with any lower mole ratiolimit described above.

The processes of the disclosure may be characterized in that the desiredcomposition of high molecular weight to low molecular weight moiety canbe achieved at any of the above hydrogen to ethylene ratios.

The process may also include “condensing agents” as is known in the artand disclosed in, for example, U.S. Pat. Nos. 4,543,399, 5,405,922 and462,999. The condensing agent, if present in the reactor can be at anylevel that will achieve the desired increase in the dew point in orderto improve cooling and ultimately space time yields. Suitable condensingagents include but are not limited to saturated hydrocarbons such aspropane, n-butane, isobutane, n-pentane, isopentane, neopentane,n-hexane, isohexane, n-heptane, n-octane or mixtures thereof.

The catalysts and catalyst systems of the invention described above aresuitable for use in any polymerization process over a wide range oftemperatures and pressures. The temperatures may be in the range of from−60° C. to about 280° C., preferably from 50° C. to about 200° C., andthe pressures employed may be in the range from 1 atmosphere to about500 atmospheres or higher.

The polymerization processes of the disclosure may be carried out insolution, in bulk, in suspension, in gas-phase, in slurry-phase, as ahigh-pressure process, or any combinations thereof. Generally solution,gas-phase and slurry-phase processes are preferred. The processes may becarried out in any one or more stages and/or in any one or more reactorhaving any one or more reaction zone and are conducted substantially inthe absence of catalyst poisons. As known by one of skill in the art,organometallic compounds may be employed as scavenging agents forpoisons to increase the catalyst activity. The polymerization processesmay be carried out batchwise, continuously run, or any combinationsthereof. In one non-limiting embodiment, the polymerization processes ofthe present disclosure are carried out in a continuous gas-phasereactor. In another non-limiting embodiment, polymerization processes ofthe disclosure are carried out in a single gas-phase reactor.

Generally, the polymers of the disclosure comprise a high molecularweight component and a low molecular weight component. The polymers ofthe disclosure generally comprise from about 0.01 to about 25% of thehigh molecular weight component, preferably from about 0.05 to about20%, more preferably from about 0.075 to about 15% of a very highmolecular weight component, even more preferably from about 0.1 to about12.5% of a very high molecular weight component, wherein the fraction ofthe high molecular weight component is determined by integrating thearea under the molecular weight vs. dwt %/d Log M curve from molecularweight=1,000,000 to molecular weight=10,000,000.

As described previously, “high molecular weight” is defined herein asbeing greater than about 1,000,000 g/mol, preferably greater than about1,500,000 g/mol, more preferably greater than about 2,000,000 g/mol, andeven more preferably greater than about 3,000,000 g/mol. In onenon-limiting embodiment, high molecular weight is greater than 5,000,000g/mol. As described previously, “low molecular weight” is defined hereinas being in the range of from about 40,000 to about 200,000 g/mol,preferably from about 50,000 to about 180,000 g/mol, more preferablyfrom about 60,000 to about 175,000 g/mol, and even more preferably fromabout 70,000 to about 150,000 g/mol. In one non-limiting embodiment, lowmolecular weight is about 100,000 g/mol.

Generally the high molecular weight component comprises a molecularweight at least 10 times greater than the low molecular weightcomponent, preferably at least 20 times greater than that of the lowmolecular weight component, more preferably at least 30 times greaterthan that of the low molecular weight component, and even morepreferably at least 40 times greater than that of the low molecularweight component.

Generally the polymers of the disclosure may have a density in the rangeof from about 0.86 g/cc to 0.97 g/cm³ as measured according to ASTM1505-03.

The resins of the disclosure generally exhibit melt strength valuesgreater than that of conventional linear or long chain branchedpolyethylene of similar melt index. As used herein “melt strength”refers to the force required to draw a molten polymer extrudate at arate of 12 mm/s² at an extrusion temperature (190° C. and 250° C. wereused herein) until breakage of the extrudate whereby the force isapplied by take up rollers. The melt strength of the polymers of thedisclosure, also referred to herein as “melt tension”, may be expressedas a function of the embodiments, the MI value may be greater than8*MI^(−0.6675). In still non-limiting embodiments, the MI value may begreater than 10*MI^(−0.6675).

In one non-limiting embodiment, the polymers of the present disclosuremay have a melt index (“MI” or “I₂”) as measured by ASTM-D-1238-E (190°C., 2.16 kg weight) in the range of from 0.001 dg/min to 25 dg/min. Inother non-limiting embodiments, the polymers of the present disclosuremay have a MI in a range of from about 0.001 dg/min to about 5 dg/min;in even other non-limiting embodiments a MI in a range of from about0.01 dg/min to about 5 dg/min in other embodiments; and in still othernon-limiting embodiments a MI in a range of from about 0.01 dg/min toabout 1 dg/min.

In one non-limiting embodiment, the polymers of the present disclosuremay have a melt flow ratio (MFR) in the range of from about 10 to 300.MFR is defined as I₂₁/I₂, wherein I₂₁ is measured by ASTM-D-1238-F, at190° C., 21.6 kg weight. In other non-limiting embodiments, the polymersof the present disclosure may have a MFR in a range of from about 15 to250; in even other non-limiting embodiments, a MFR in a range of fromabout 15 to 200; and in still other non-limiting embodiments a MFR in arange of from about 20 to 150.

As known by one of skill in the art, when subjected to uniaxialextension at a given strain rate, the extensional viscosity of a polymerincreases with time. As also known by one of skill in the art, thetransient uniaxial extensional viscosity of a linear polymer can bepredicted. Strain hardening occurs when a polymer is subjected touniaxial extension and the transient extensional viscosity increasesmore than what is predicted from linear viscoelastic theory. As definedherein, the strain hardening index is the ratio of the observedtransient uniaxial extensional viscosity to the theoretically predictedtransient uniaxial extensional viscosity. Strain hardening index isexpressed herein as the following ratio:η_(E) ⁺observed/η_(E) ⁺predicted.At conditions characteristic of film blowing, for example strain rate of1 sec⁻¹, temperature of 190° C., and time of 4 seconds (i.e., a strain(c) of 4), generally the strain hardening index of the polymers of thepresent disclosure is a ratio/value greater than 3 in some embodiments,a value greater than 5 in other embodiments, a value greater than 8 ineven other embodiments, and a value greater than 10 in still otherembodiments.

The polymers of the present disclosure may be characterized in that theyexhibit an activation energy (Ea) of less than 7 kcal/mol/K. In othernon-limiting embodiments, the Ea of the polymers of the presentdisclosure may be less than 6 kcal/mol/K.

In the present disclosure, the activation energy is determined fromdynamic oscillatory shear rheology measurements at five differenttemperatures, 150° C., 170° C., 190° C., 210° C., 230° C. and 250° C. Ateach temperature, scans are performed as a function of angular shearfrequency (from ω=100 rad/s to ω=0.01 rad/s) at a constant shear strain.Master curves of storage modulus, G′, and loss modulus, G″, are obtainedby time-temperature (t-T) superposition and the flow activation energies(E_(a)) are obtained from an Arrhenius plot, a_(T)=exp(E_(a)/kT), where1/T is plotted as a function of ln(a_(T)), which relates the shiftfactor (a_(T)) to E_(a).

As known by one of skill in the art, rheological data may be presentedby plotting the phase angle versus the absolute value of the complexshear modulus to produce a van Gurp-Palmen (vGP) plot. The vGP plot ofconventional polyethylene polymers shows monotonic behavior and anegative slope toward higher G* values. Conventional LLDPE polymer bothwith and without long chain branches also exhibit a negative slope on avGP plot. The vGP plots of the polymers described in the presentdisclosure exhibit two slopes—a positive slope at lower G* values and anegative slope at higher G* values.

Referring now to FIG. 1, there are shown van Gurp-Palmen (vGP or VGP)plots of various linear polyethylene resins: a conventionalmonodispersed PE (hydrogenated polyputadiene) (closed circles), aconventional metallocene LLDPE resin with a narrow molecular weightdistribution (closed squares), a conventional bimodal resin having abroad molecular weight distribution (asterisk), and an inventive resinof the disclosure (closed diamonds). The molecular weights and molecularweight distributions of the conventional resins are shown in Table 1below. Increasing polydispersity in comparative conventional resinsstretches the curve along the abscissa, but does not change themonotonic nature of the vGP plot (note how their curves in FIG. 1 becomeless steep). The resin (Exceed™ 1018) and the bimodal resin (Borouge™ FB2230) are commercially available resins. In non-limiting embodiments ofthe present disclosure, the introduction of a high molecular weightfraction according to the disclosure may change the shape of the vGPplot in that it causes a maximum in the vGP plot as shown in FIG. 1.

TABLE 1 Resin Grade Mw Mw/Mn Anionically polymerized  87,400 g/mol 1.02hydrogenated polybutadiene Metallocene PE resin Exceed ™ 1018 101,000g/mol 2.2 Dual reactor bimodal PE Borouge ™ FB 192800 20.4 resin 2230

In non-limiting embodiments, the ratio of the z-average molecular weight(Mz) to the weight average molecular weight (Mw) of the polymers of thepresent disclosure may be a ratio having a value in a range of fromabout 6 to 12. In other non-limiting embodiments, the Mz/Mw ratio may bea value in a range of from about 7 to 15. In even other non-limitingembodiments, the Mz/Mw ratio may be a value greater than 10. The ratioof the Mw to the number average molecular weight (Mn) (ratio of Mw/Mn isalso referred to as polydispersity) can be in the range of from 2.5 to 8in some non-limiting embodiments, from 3.0 to 10 in other non-limitingembodiments, and from 3.5 to 12 in even other non-limiting embodiments.Generally for the polymers of the disclosure, the Mz/Mw ratio is a valuegreater than the Mw/Mn ratio. As known in the art, Mn is the numberaverage molecular weight and may be expressed as Σ(M_(i)N_(i))/ΣN_(i);Mw is the weight average molecular weight and may be expressed asΣ(M_(i) ²N_(i))/Σ(M_(i)N_(i)); and Mz is the z-average molecular weightof a polymer and may be expressed as Σ(M_(i) ³N_(i))/Σ(M_(i) ²N_(i))wherein Ni is the number of molecules of molecular weight Mi. Techniquesfor determining these values are known in the art and any may be usedherein.

The polymers of the disclosure generally show very high viscosities atlow shear rates and exhibit strong shear thinning. A shear thinningindex may be expressed as the ratio of the complex viscosities (η*) attwo given oscillatory shear frequencies, arbitrarily selected herein tobe 0.01 rad/sec (η*_(0.01)) and 100 rad/sec (η*₁₀₀). Thus, the shearthinning index is expressed herein as (η*_(0.01))/(η*₁₀₀). Both(η*_(0.01)) and (η*₁₀₀) are obtained from oscillatory shear rheometry asdescribed herein. The shear thinning index (η_(0.01)/η*₁₀₀) of thepolymers of the present disclosure may be a value in the range of 5 to500. In other non-limiting embodiments, the shear thinning index may bein the range of 25 to 500. In even other embodiments, the shear thinningindex may be in the range of 50 to 500. In still other embodiments, theshear thinning index may be in the range of 100 to 500.

The resins of the disclosure are suitable for use in a variety ofproducts and end-use applications including, but not limited to film,sheets, laminating, jacketing, insulating, and a variety of articlesproduced by injection molding, blow molding, extrusion coating, profileextrusion, and combinations thereof.

EXAMPLES

It is to be understood that while the invention has been described inconjunction with the specific embodiments thereof, the foregoingdescription is intended to illustrate and not limit the scope of theinvention. Other aspects, advantages and modifications will be apparentto those skilled in the art to which the invention pertains.

Therefore, the following examples are put forth so as to provide thoseskilled in the art with a complete disclosure and description of how tomake and use the compounds of the invention, and are not intended tolimit the scope of that which the inventors regard as their invention.Because of the high molecular weights of the polyethylene resinsdescribed herein, it is necessary to measure size exclusionchromatography at elevated temperatures to ensure adequate solubility ofthe polymer molecules. Molecular weights and molecular weightdistributions of the resins described herein were determined using hightemperature size exclusion chromatography.

Measurements of Molecular Weights and Molecular Weight Distributions

The molecular weights and molecular weight distributions of the resinsdescribed in the present disclosure were characterized using a HighTemperature Size Exclusion Chromatograph (PL 220, Polymer Laboratories),equipped with a differential refractive index detector (DRI). ThreePolymer Laboratories PLgel 10 mm Mixed-B columns were used. The nominalflow rate was 1.0 cm³/min, and the nominal injection volume was 300 μL.The various transfer lines, columns and differential refractometer (theDRI detector) were contained in an oven maintained at 160 C.

Polymer solutions were prepared in filtered 1,2,4-Trichlorobenzene (TCB)containing 1000 ppm of butylated hydroxy toluene (BHT). The same solventwas used as the SEC eluent. Polymer solutions were prepared bydissolving the desired amount of dry polymer in the appropriate volumeof SEC eluent to yield concentrations ranging from 0.5 to 1.5 mg/mL. Thesample mixtures were heated at 160° C. with continuous agitation forabout 2 to 2.5 hours. Sample solution will be filtered off-line beforeinjecting to GPC with 2 μm filter using the Polymer Labs SP260 SamplePrep Station.

The separation efficiency of the column set was calibrated using aseries of narrow MWD polystyrene standards, which reflects the expectedMW range for samples and the exclusion limits of the column set.Eighteen individual polystyrene standards, ranging from Mp ˜580 to10,000,000, were used to generate the calibration curve. The polystyrenestandards are obtained from Polymer Laboratories (Amherst, Mass.). Toassure internal consistency, the flow rate is corrected for eachcalibrant run to give a common peak position for the flow rate marker(taken to be the positive inject peak) before determining the retentionvolume for each polystyrene standard. The flow marker peak position thusassigned was also used to correct the flow rate when analyzing samples;therefore, it is an essential part of the calibration procedure. Acalibration curve (log Mp vs. retention volume) is generated byrecording the retention volume at the peak in the DRI signal for each PSstandard, and fitting this data set to a 2^(nd)-order polynomial. Theequivalent polyethylene molecular weights are determined by using thefollowing Mark-Houwink coefficients:

k (dL/g) A PS 1.75 × 10−4 0.67 PE 5.79 × 10−4 0.695Dynamic Rheology

For dynamic oscillatory shear measurements, the resins were stabilizedwith 500 ppm of Irganox 1076 and 1500 ppm of Irgafos168. Themeasurements were carried out on an oscillatory rheometer (RheometricsRDS-2, ARES) with 25 mm diameter parallel plates in a dynamic mode undernitrogen atmosphere. For all experiments, the rheometer was thermallystable at 190° C. for at least 30 minutes before insertingcompression-molded sample of resin onto the parallel plates. Todetermine the samples viscoelastic behavior, frequency sweeps in therange from 0.01 to 100 rad/s were carried out at 190° C. under constantstrain. To determine the activation energy, the sweeps were carried outat 5 different temperatures as described herein.

Structures of Precatalysts and Ligands

Anhydrous oxygen free solvents were used. Thirty-weight percentmethylaluminoxane (MAO) and (1-Me, 3-BuCp)₂ZrCl₂ were obtained fromAlbemarle Corporation. (n-PrCp)₂HfCl₂ was obtained from BoulderScientific. (n-PrCp)₂HfMe₂ may be prepared by methylation of(n-PrCp)₂HfCl₂ with methyl lithium in toluene. Ligand B was obtainedfrom Symyx Technologies. Zr(CH₂Ph)₂Cl₂(OEt₂) was prepared by reaction ofZrBnz₄ and ZrCl₄ in diethyl ether. Catalyst E is a non-inventivesupported catalyst prepared from Precat D, MAO and support used as astandard in gas-phase polymerizations to insure the reactor is runningproperly.

Example 1 Preparation of Ligand A

STEP 1. A solution of 30 g (0.13 mol, 1 eq) of O-MOM-bromo methylcompound in 300 ml of dry tetrahydrofuran was cooled to −76° C. 53 ml ofn-butyl lithium (1.2 eq, 0.155 mol) was added in such a manner that thetemperature did not rise beyond −70° C. The resulting mixture wasstirred for another 4 hours at −78° C. 53 ml (0.18 mol, 1.4 eq) ofn-butyl borate was then added to the reaction mass maintaining thetemperature from −76° C. to −70° C. Stirring was then continued foranother 5 hours after which the reaction mass was quenched with 150 mlof water. This was stirred for another 10 hrs. The organic layer and theaqueous layer were separated. The aqueous layer was washed withpetroleum ether and the organic layer was washed with 10% sodiumhydroxide solution. The aqueous layer and the sodium hydroxide layerwere then combined and acidified using 505 conc. HCl solution. A whitesolid was obtained which was filtered off and dried under vacuum.Yield=20 g.

STEP 2. 15 g (0.067 mol, 1 eq) of 1-Bromo-2-methyl naphthalene, 0.4 g (5mol %) of palladium tetrakis, 16 g (0.08 μmol, 1.2 eq) of —O-MOM boronicacid, 29 g of 2M solution of sodium carbonate and 150 ml of toluene weretaken in a RB flask and heated to 120° C. After 16 hrs, the reactionmass was diluted with ethyl acetate and the two layers were separated.The resulting organic layer was washed with water followed by brine.This was then dried over sodium sulfate, filtered and concentrated. Thecrude obtained (25 g) was then taken for further step without anypurification.

STEP 3. The 25 g of crude material obtained from STEP 2 was stirredalong with 240 ml of methanolic HCl solution at RT for 16 hrs. Thereaction mass was then diluted with excess of ethyl acetate. The organiclayer was then washed with water followed by brine. This was then driedover sodium sulfate, filtered and concentrated. The crude obtained wasthen purified by column chromatography using 1% of ethyl acetate inpetroleum ether. Yield=11.8 g.

STEP 4. 11.8 g (0.047 mol, 1 eq) of methynaphthyl phenol obtained fromthe above step and 7 ml (0.047 mol, 1 eq) of triethyl amine were takenin 110 ml of dry dichloromethane and stirred well. A solution of 13 g(0.007 mol, 1.5 eq) of N-bromo succinimide in 300 ml of drydichloromethane was added over a period of 30 mins. The reaction masswas then stirred for 24 hours after which it was quenched with 1.5N HCl.The organic layer was separated and washed with water and brine. It wasthen dried over sodium sulfate and concentrated. The crude obtained (17g) was then taken for further step without any purification as it waspure enough. (98%).

STEP 5. To a solution of 17 g (0.052 mol, 1 eq) of the bromo phenolcompound and 43 ml (0.26 mol, 5 eq) of diisopropyl ethyl amine in 170 mlof dry dichloromethane, 16 ml (0.208 mol, 4 eq) of MOM chloride wasadded in drops. The resulting mass was stirred at RT for 16 hrs. Thereaction mass was diluted with 1.5N HCl solution. The organic layer wasseparated and washed with water and brine. It was then dried over sodiumsulfate and concentrated. The crude obtained was purified by columnchromatography using petroleum ether and ethyl acetate as eluant whichwas 99% pure by HPLC. This was taken for the further step. Yield=12 g.

STEP 6. A solution of 12 g (0.0323 mol, 1 eq) of O-MOM-bromo compound in120 ml of dry tetrahydrofuran was cooled to −76° C. To this 13.5 ml ofn-butyl lithium (1.2 eq, 0.034 mol) was added in such a manner that thetemperature did not rise beyond −70° C. The resulting mixture wasstirred for another 1 hr at −78° C. 13 ml (0.045 mol, 1.4 eq) of n-butylborate was then added to the reaction mass maintaining the temperaturefrom −76° C. to −70° C. The reaction mass was then quenched with 50 mlof water and extraction was done in ethyl acetate. This was dried oversodium sulfate, filtered and concentrated. The crude (11 g) obtained wastaken along with 3.7 g (10 mol %) of palladium tetrakis, 3.8 g (0.008mol) of C3 iodo ether (prepared from the 2-iodophenol and1,2-dibromopropane), 27 g (0.258 mol, 8 eq) of 2M solution of sodiumcarbonate and 120 ml of toluene, in a RB flask and heated to 120° C.After 16 hrs, the reaction mass was diluted with ethyl acetate and thetwo layers were separated. The resulting organic layer was washed withwater followed by brine. This was then dried over sodium sulfate,filtered and concentrated. The crude obtained (17 g) was then taken forfurther step without any purification.

STEP 7. The 17 g of crude material obtained from STEP 6 was stirredalong with 170 ml of methanolic HCl solution and 3 ml of dichloromethaneat RT for 16 hrs. The reaction mass was then diluted with excess ofethyl acetate. The organic layer was then washed with water followed bybrine. This was then dried over sodium sulfate, filtered andconcentrated. The crude obtained was then purified by columnchromatography using 1% of ethyl acetate in petroleum ether. Twofractions were collected and analyzed by HPLC, NMR and LCMS. The firstfraction was 4 g and consisted of two isomers which were confirmed byNMR, LCMS AND HPLC. The second fraction (550 mg) also consists of twoisomers which were confirmed by NMR and LCMS.

Example 2 Preparation of Precatalyst A

To a solution consisting of Ligand A (2.750 grams, 3.814 mmol) inapproximately 80 milliliters of toluene was added a solution ofZr(CH₂Ph)₂Cl₂(Et₂O) (1.603 grams) in 20 milliliters of toluene. Anadditional 20 milliliters of solvent were added to the mixture. Afterstirring the mixture at room temperature for 1 hour, the reaction washeated to 80° C. for 2 hours. Approximately 70% of the solvent wasremoved, and pentane added to induce further precipitation of theproduct. The mixture was chilled. The solids collected by filtration andwashed with minimum pentane.

Example 3 Preparation of Precatalyst B

A solution of Zr(CH₂Ph)₂Cl₂(Et₂O)₁₂ (58.7 mg, 0.1355 mmol) in toluene (8mL) was added to a hot solution (120° C.) of Ligand B (100 mg, 0.129mmol) in toluene (32 mL) over a period of 5 minutes while stirring.After 15 min, the reaction was chilled and the solvent mostly removed.When there was 1-2 mL left, the solution was placed in about 15 mL ofpentane. The solvents were reduced to ca ½ of the original volume. Theslurry was decanted and the solids dried. Yield 39 mg.

Example 4 Preparation of Methyl Aluminoxane Supported on Silica (SMAO)

In a typical procedure, Crosfield ES757 silica (741 g), dehydrated at600° C., was added to a stirred (overhead mechanical conical stirrer)mixture of toluene (2 L) and 30 wt % solution of methyl aluminoxane intoluene (874 g, 4.52 mol). The silica was chased with toluene (200 mL)then the mixture was heated to 90° C. for 3 h. Afterwards, volatileswere removed by application of vacuum and mild heat (40° C.) overnightthen the solid was allowed to cool to room temperature.

Examples 5-21 Supported Catalyst Preparations

A solution of precatalysts (PC) and toluene was added at a rate of ca0.5 mL/min to a slurry SMAO and pentane (amounts provided in Table 2below), stirred with an overhead stirrer. After stirring for >30 min,the mixture was filtered and dried in-vacuo.

TABLE 2 Supported Catalyst preparations Mass Mass of of PC 1 PC 2 SMAOToluene Pentane mol % Example # PC 1 (mg) PC 2 (g) (g) (mL) (mL) PC 1  5A 1.4 D 1.3044 80.03 60 450 0.05  6 A 2.6 D 1.3 80.02 60 450 0.1  7 A1.3 D 0.6469 40.01 30 375 0.1  8 B 6.7 D 0.647 40 30 375 0.48  9- D0.8136 50.06 40 450 0 Comparative 10 B 1.9 D 0.8133 50.07 30 375 0.11 11A 1.5 D 0.8166 50 40 450 0.09 12 A 7.8 D 0.811 50 30 375 0.47 13 B 7.1 D0.8113 50 30 375 0.4 14- D 0.814 50 40 450 0 Comparative 15 B 1.4 D0.5877 40.1 30 375 0.11 16 A 1.7 D 0.8127 50.02 40 450 0.1 17- C 0.794150 20 300 0 Comparative 18 A 1.3 C 0.6337 39.99 50 450 0.1 19 A 3.3 C0.6339 39.95 65.4 450 0.25 20 A 6.6 C 0.6363 39.9 90.8 450 0.5

Examples 22-42 Polymerization Testing in a Continuous Fluidized BedReactor

These catalysts were tested in a continuous fluidized-bed gas-phasereactor with a nominal 14″ reactor diameter, an average bed weight ofabout 1900 g, gas-velocity of about 1.6 ft/s, production rate of about500 g/h. The reactor was operated at a temperature of 79.4° C., and apressure of 300 psig. The composition of ethylene, hydrogen, and1-hexene is indicated in Table 3 below; the balance being nitrogen.

TABLE 3 Summary of Polymerization conditions Catalyst Comonomer C2 fromH2 conc. conc. conc. Residence Example Example (molppm) (mol %) (mol %)Time (h) 21- E 251 1.083 35.0 3.8 comparative 22  5 246 1.109 35.0 4.223  6 244 1.097 35.0 3.6 24- E 123 0.619 34.7 4.0 comparative 25- E 890.618 35.0 4.7 comparative 26  7 85 0.627 35.0 3.7 27  8 94 0.725 35.14.3 28  8 90 0.679 34.7 3.8 29-  9 91 0.342 35.2 5.0 comparative 30 1099 0.312 35.1 5.7 31 11 97 0.291 35.0 3.7 32 12 103 0.282 35.0 4.0 33 13102 0.320 35.0 4.2 34- 14 and 9  85 0.179 35.0 4.2 comparative 35 15 and10 84 0.171 35.0 3.3 36 16 and 11 82 0.178 35.0 3.3 37 13 86 0.197 35.05.0 38- E 84 0.057 35.0 6.0 comparative 39- 17 115 0.019 35.0 4.1comparative 40 18 115 0.003 35.0 4.0 41 19 117 0.009 35.0 4.3 42 20 1140.003 35.0 4.4

Example 43 Catalyst Evaluation/Polymer Production in LGPR

The test catalysts were evaluated in a continuous run gas phase reactorR125 (LGPR). The reactor was lined out with standard E catalyst atconditions used to make 1.2 MI, 0.917 density (LGPR condition 51-2006).Product was collected and the reactor was transitioned to each of theother catalysts.

Ethylene/1-hexene copolymers were produced according to the followingprocedure. The catalyst composition was injected dry into a fluidizedbed gas phase polymerization reactor. More particularly, polymerizationwas conducted in a 152.4 mm diameter gas-phase fluidized bed reactoroperating at approximately 2068 kPa total pressure. The reactor bedweight was approximately 2 kg. Fluidizing gas was passed through the bedat a velocity of approximately 0.6 m per second. The fluidizing gasexiting the bed entered a resin disengaging zone located at the upperportion of the reactor. The fluidizing gas then entered a recycle loopand passed through a cycle gas compressor and water-cooled heatexchanger. The shell side water temperature was adjusted to maintain thereactor temperature as specified in Tables 4-8. Ethylene, hydrogen,1-hexene and nitrogen were fed to the cycle gas loop just upstream ofthe compressor at quantities sufficient to maintain the desired gasconcentrations as specified in Tables 4-8. Gas concentrations weremeasured by an on-line vapor fraction analyzer. Product (polyethyleneparticles) was continuously withdrawn from the reactor in batch modeinto a purging vessel before it was transferred into a product bin.Residual catalyst and activator in the resin was deactivated in theproduct drum with a wet nitrogen purge. The catalyst was fed to thereactor bed through a stainless steel injection tube at a ratesufficient to maintain the desired polymer production rate. “C₆/C₂ flowratio (“FR”)” is the ratio of the lbs of 1-hexene comonomer feed to thepounds of ethylene feed to the reactor, whereas the C₆/C₂ ratio is theratio of the gas concentration of 1-hexene moles in the cycle gas to thegas concentration of ethylene moles in the cycle gas. The C₆/C₂ ratio isobtained from a cycle gas vapor fraction analyzer, whereas the C₆/C₂Flow Ratio comes from some measure of the mass flow. The cycle gas isthe gas in the reactor, and is measured from a tap off the recirculatingloop around the reactor. The ratios reported in the following tables arefrom the gas concentrations in the reactor. Samples are taken every 9min, and thus reported C₆/C₂ ratios are running averages. Tables 4-8provide summaries of run conditions and product properties ofnon-limiting examples of the present disclosure for resins withdensities of 0.91-0.95 as indicated in the tables.

The MI and HLMI values reported in Tables 4-8 as “QC, reactor granules”were obtained from the polymer granules that were isolated from thepolymerization reactor. Each granular resin was dry-blended with 1500ppm BHT (2,6-bis(1,1-dimethylethyl)-4-methylphenol). MI and HLMI werethen measured according to ASTM-D-1238-E and ASTM D-1238-F,respectively.

The MI and HLMI values reported in Tables 4-8 as “ASTM, pellets” wereobtained from compounded resins. To compound the resins, 500 ppm Irganox1076 and 1500 ppm Igrafos 168 (both available from Ciba Chemicals) wereadded to the reactor granules and the admixture extruded using a ¾″Haake twin screw extruder. The melt temperature was 210° C. The outputrate was about 3.5 lbs/hr. The MI and HLMI of the pellets were thenmeasured according to ASTM-D-1238-E and ASTM D-1238-F, respectively.

The density values reported in Tables 4-8 as “QC, reactor granules” wereobtained from the polymer granules that were isolated from thepolymerization reactor. Each granular resin was dry-blended with 1500ppm BHT and compression molded plaques were produced by heating thepolymers in a mold to 179° C. and subsequently cooling them to 23° C. ata rate of 15° C. The molding pressure was chosen such that air pocketsare removed and a uniform samples result. The density was thendetermined by immersing solid specimens of the compression moldedplaques in a column filled with liquid of uniformly gradient density.The gradient density was in accordance with ASTM 1505.

The density values reported in Tables 4-8 as “ASTM, pellets” wereobtained from compounded resins. To compound the resins, 500 ppm Irganox1076 and 1500 ppm Igrafos 168 were added to the reactor granules and theadmixture extruded using a ¾″ Haake twin screw extruder. The melttemperature was 210° C. The output rate was about 3.5 lbs/hr. Thedensity of the pellets was then measured according to ASTM 1505-03.

TABLE 4A Summary of Process Data - resin density 0.91 Example 21 22 23Catalyst from Example E 5 6 PROCESS DATA H2 conc. (molppm) 251 246 244Hydrogen flow (sccm) 6.72 6.22 6.88 Comonomer conc. (mol %) 1.083 1.1091.097 C2 conc. (mol %) 35.0 35.0 35.0 Comonomer/C2 Flow Ratio 0.1350.135 0.135 C2 flow (g/hr) 590 606 624 H2/C2 Ratio 7.2 7.0 7.0Comonomer/C2 Ratio 0.031 0.032 0.031 Rx. Pressure (psig) 300 300 300Reactor Temp (F.) 175 175 175 Avg. Bedweight (g) 1894 1930 1903Production (g/hr) 494 462 533 Residence Time (hr) 3.8 4.2 3.6 C2Utilization (gC2/gC2 poly) 1.19 1.31 1.17 Avg Velocity (ft/s) 1.58 1.571.46 Catalyst Timer (minutes) 15.0 50.0 38.0 Catalyst Feed (g/hr) 0.6940.208 0.274 Cat Prod. (g/g) - 496 1546 1356 MB (new = .249) Product DataBulk Density 0.3565 0.3993 Powder Flow Time 7.63 7.25 Total Production(grams) 26978 12717 18669 Number of Bedturnovers 14.2 6.6 9.8 BasicResin Data (QC) MI (QC reactor granules) 5.92 5.47 4.51 HLMI (QC reactorgranules) 112.31 104.81 HLMI/MI (QC reactor 18.97 23.24 granules)Density (QC reactor granules) 0.9115 0.9107 0.9105

TABLE 4B Summary of Resin Data - resin density 0.91 Example 21 22 23Catalyst from Example Product Data E 5 6 Resin 00270-153 020 030 040 MI(ASTM, pellets) 5.69 5.31 4.4 HLMI (ASTM, pellets) 112.70 100.10 83.7HLMI/MI (ASTM, pellets) 18.90 18.90 18.8 Density (ASTM, pellets) 0.91240.9110 0.9118

TABLE 5A Summary of Process Data - resin density 0.92 Example 24 25 2627 28 Catalyst from Example E E 7 8 8 PROCESS DATA H2 conc. (molppm) 12389 85 94 90 Hydrogen flow (sccm) 4.22 1.75 1.45 1.45 1.45 Comonomerconc. (mol %) 0.619 0.618 0.627 0.725 0.679 C2 conc. (mol %) 34.7 35.035.0 35.1 34.7 Comonomer/C2 Flow Ratio 0.088 0.085 0.084 0.084 0.084 C2flow (g/hr) 631 546 647 504 660 H2/C2 Ratio 3.5 2.5 2.4 2.7 2.6Comonomer/C2 Ratio 0.018 0.018 0.018 0.021 0.020 Rx. Pressure (psig) 300300 300 300 300 Reactor Temp (F.) 175 175 175 175 175 Avg. Bedweight (g)1946 1852 1834 1824 1937 Production (g/hr) 491 397 497 427 505 ResidenceTime (hr) 4.0 4.7 3.7 4.3 3.8 C2 Utilization (gC2/gC2 poly) 1.29 1.371.30 1.18 1.31 Avg Velocity (ft/s) 1.51 1.53 1.45 1.53 1.52 CatalystTimer (minutes) 17.5 20.0 20.0 14.0 16.0 Catalyst Feed (g/hr) 0.5960.521 0.521 0.744 0.651 Cat Prod. (g/g) - MB (new = .249) 574 532 665400 541 Product Data Melt Index (MI) (QC reactor 2.22 1.21 0.69 0.120.12 granules) HLMI (QC reactor granules) 39.05 21.56 13.40 2.03 n/aHLMI/MI Ratio 17.59 17.82 19.42 16.92 n/a Gradient Density (QC reactor0.9186 0.9174 0.9176 0.9181 0.9177 granules) Bulk Density n/a 0.3718 n/a0.3980 n/a Powder Flow Time n/a 7.7 7.5 7.3 n/a Total Production (grams)7853.0 8738.0 10929.0 8536.0 10096.0 Number of Bedturnovers 4.0 4.7 6.04.7 5.2 NOTES Trouble with H2 cat feeder analyzer and H2 problems at endflow control of run.

TABLE 5B Summary of Resin Data - resin density 0.92 Data Point 050-2006051-2006 052-2006 054-2006 055-2006 Example 24 25 26 27 28 Catalyst fromExample E E 7 8 8 Product Data Resin 00270-128 no sample 100 MI (ASTM,pellets) 1.33 0.6 0.7 0.1 0.1 HLMI (ASTM, pellets) 22.17 13.5 14.0 5.55.3 HLMI/MI 16.66 22.9 20.2 68.1 57.0 Density (ASTM, pellets) 0.91710.9164 0.9167 0.9172 0.9171 Melt Strength (190 C.) 13.10 18.60 15.8017.10 too high Melt Strength (250 C.) 6.10 9.60 8.90 10.00 34.90 ShearThinning Index 3.40 21.90 8.70 99.70 166.80 Strain Hardening Index 1.126.80 4.64 8.68 250.78 Ea No data No data No data No data No data GPC-3dMw 40033 35164 42025 47289 49199 Mw 105638 130295 147701 245554 243126Mz 189208 720683 864299 1719040 1915233 Mw/Mn 2.64 3.71 3.51 5.19 4.94Mz/Mw 1.79 5.53 5.85 7.00 7.88

TABLE 6A Summary of Process Data - resin density 0.93 Example 29 30 3132 33 Catalyst from Example 9 10 11 12 13 Process Data H2 conc. (molppm)91 99 97 103 102 Hydrogen flow (sccm) 20.09 4.29 3.60 5.14 2.73Comonomer conc. (mol %) 0.342 0.312 0.291 0.282 0.320 C2 conc. (mol %)35.2 35.1 35.0 35.0 35.0 Comonomer/C2 Flow Ratio 0.035 0.035 0.035 0.0350.035 C2 flow (g/hr) 707 602 689 718 711 H2/C2 Ratio 2.6 2.8 2.8 2.9 2.9Comonomer/C2 Ratio 0.010 0.009 0.008 0.008 0.009 Rx. Pressure (psig) 300300 300 300 300 Reactor Temp (F.) 175 175 175 175 175 Avg. Bedweight (g)1864 1865 1878 1932 1939 Production (g/hr) 375 330 508 487 459 ResidenceTime (hr) 5.0 5.7 3.7 4.0 4.2 C2 Utilization (gC2/gC2 poly) 1.89 1.821.36 1.48 1.55 Avg Velocity (ft/s) 1.57 1.58 1.58 1.58 1.58 CatalystTimer (minutes) 28.0 24.4 20.0 23.2 23.0 Catalyst Feed (g/hr) 0.3720.426 0.521 0.449 0.453 Cat Prod. (g/g) - MB (new = .249) 703 540 680756 707 Bulk Density 0.4018 0.4103 0.4178 0.4298 0.4360 Powder Flow Time7.16 7.78 8.10 9.22 9.32 Total Production (grams) 28274 15410 1438520990 15082 Number of Bedturnovers 15.2 8.3 7.7 10.9 7.8 Basic ResinData MI (QC reactor granules) 1.25 1.1 0.9 0.7 0.1 HLMI (QC reactorgranules) 22.32 21.8 21.1 19.4 9.0 HLMI/MI 17.80 19.9 23.2 26.7 100.8Density (QC reactor granules) 0.9285 0.9294 0.9305 0.9310 0.9280

TABLE 6B Summary of Resin Data - resin density 0.93 Data Point 5-2_20075-3_2007 5-4_2007 5-5_2007 5-6_2007 Example 29 30 31 32 33 Catalyst fromExample 9 10 11 12 13 Resin 00270-136 100 200 300 400 500 MI (ASTM,pellets) 1.25 1.1 0.9 0.7 0.1 HLMI (ASTM, pellets) 22.32 21.8 21.1 19.49.0 HLMI/MI 17.80 19.9 23.2 26.7 100.8 Density (ASTM, pellets) 0.92850.9294 0.9305 0.9310 0.9280 Melt Strength (190 C.) 13.10 18.60 15.8017.10 too high Melt Strength (250 C.) 6.10 9.60 8.90 10.00 34.90 ShearThinning Index 21.97 No data No data 248.23 Strain Hardening Index 4.004.41 5.42 4.41 14.48 Ea 7.02 No data No data 5.57 GPC-3d Mw 37426 3603236872 31984 42374 Mw 120938 136675 138060 162940 265891 Mz 6833801022488 1047292 1285485 2227940 Mw/Mn 3.23 3.79 3.74 5.09 6.27 Mz/Mw5.65 7.48 7.59 7.89 8.38

TABLE 7A Summary of Process Data - resin density 0.94 Example 34 35 3637 Catalyst from Example 14 and 9 15 and 10 16 and 11 13 PROCESS DATA H2conc. (molppm) 85 84 82 86 Hydrogen flow (sccm) 7.37 7.54 6.04 3.97Comonomer conc. (mol %) 0.179 0.171 0.178 0.197 C2 conc. (mol %) 35.035.0 35.0 35.0 Comonomer/C2 Flow Ratio 0.020 0.020 0.020 0.020 C2 flow(g/hr) 736 739 635 408 H2/C2 Ratio 2.4 2.4 2.4 2.5 Comonomer/C2 Ratio0.005 0.005 0.005 0.006 Rx. Pressure (psig) 300 300 300 300 Reactor Temp(F.) 175 175 175 175 Avg. Bedweight (g) 1844 1917 1857 1909 Production(g/hr) 443 588 567 380 Residence Time (hr) 4.2 3.3 3.3 5.0 C2Utilization (gC2/gC2 poly) 1.66 1.26 1.12 1.07 Avg Velocity (ft/s) 1.481.46 1.46 1.46 Catalyst Timer (minutes) 18.0 19.0 16.3 22.0 CatalystFeed (g/hr) 0.578 0.548 0.641 0.473 Cat Prod. (g/g) - MB(new = .249) 534748 617 560 Product Data Bulk Density 0.4128 0.4500 0.4353 0.4478 PowderFlow Time 8.40 9.29 7.41 8.81 Total Production (grams) 16222 14429 1646315649 Number of Bedturnovers 8.8 7.5 8.9 8.2 Basic Resin Data MI (QCreactor granules) 1.81 1.75 1.45 1.28 HLMI (QC reactor granules) 36.1934.26 30.36 28.25 HLMI/MI 20.03 20.03 20.03 20.03 Density (QC reactorgranules) 0.9354 0.9373 0.9373 0.9377

TABLE 7B Summary of Resin Data - resin density 0.94 Example 34 35 36 37Catalyst from Example 14 and 9 15 and 10 16 and 11 13 Product Data MI(ASTM, 1.81 1.75 1.45 1.28 pellets) HLMI (ASTM, 36.19 34.26 30.36 28.25pellets) HLMI/MI 20.03 20.03 20.03 20.03 Density 0.9381 0.9375 0.93790.9378 (ASTM, pellets) Melt Strength 13.10 18.60 15.80 too high (190 C.)Melt Strength 6.10 9.60 8.90 34.90 (250 C.) Shear 5.37 4.63 19.82 80.60Thinning Index Strain n/a 1.00 4.14 16.64 Hardening Index Ea in progressin progress in progress GPC-3d Mn 26352 29682 27576 28242 Mw 90911 9385194584 125147 Mz 170268 176178 240151 769345 Mw/Mn 3.45 3.16 3.43 4.43Mz/Mw 1.87 1.88 2.54 6.15

TABLE 8A Summary of Process Data - resin density 0.95 Data Point 303-153303-154 303-155 303-156 Example 38 39 40 41 42 Catalyst from Example E17 18 19 20 Start Time 1700 1500 1900 300 2300 Finish Time next day 1100same 500 700 1100 same day 1500 day PROCESS DATA H2 conc. (molppm) 84115 115 117 114 Hydrogen flow (sccm) 7.61 3.37 3.32 3.28 3.04 Comonomerconc. (mol %) 0.057 0.019 0.003 0.009 0.003 C2 conc. (mol %) 35.0 35.035.0 35.0 35.0 Comonomer/C2 Flow Ratio 0.007 0.003 0.003 0.003 0.003 C2flow (g/hr) 587 647 632 646 608 H2/C2 Ratio 2.4 3.3 3.3 3.3 3.3Comonomer/C2 Ratio 0.002 0.001 0.00007 0.00027 0.00007 Rx. Pressure(psig) 300 300 300 300 300 Reactor Temp (F.) 175 175 175 175 175 Avg.Bedweight (g) 1864 1881 1879 1910 1897 Production (g/hr) 313 457 472 446432 Residence Time (hr) 6.0 4.1 4.0 4.3 4.4 C2 Utilization (gC2/gC2poly) 1.87 1.42 1.34 1.45 1.41 Avg Velocity (ft/s) 1.57 1.56 1.56 1.551.56 Catalyst Timer (minutes) 15.0 45.0 45.0 45.0 43.0 Catalyst Feed(g/hr) 0.694 0.231 0.231 0.231 0.242 Cat Prod. (g/g) - 314 1377 14221343 1243 MB (new = .249) Product Data Bulk Density 0.4200 0.4038 0.40930.4057 0.3884 Powder Flow Time 6.81 7.88 7.34 7.15 6.81 Total Production(grams) 15531 33596 15131 13092 26301 Number of Bedturnovers 8.3 17.98.1 6.9 13.9 Basic Resin Data MI 1.32 0.92 0.81 0.37 0.21 HLMI 20.6018.27 13.96 12.18 9.29 HLMI/MI 15.54 19.86 17.17 32.91 44.24 Density0.9469 0.9467 0.9485 0.9497 0.9488

TABLE 8B Summary of Resin Data - resin density 0.94 Product Data from Ex38 39 40 41 42 Resin 00270-157 020 030 040 050 060 MI (ASTM, pellets)1.59 1.17 0.97 0.68 0.43 HLMI (ASTM, pellets) 29.50 19.00 16.80 14.4010.97 HLMI/MI (ASTM, pellets) 18.55 16.24 17.32 21.18 25.51 Density(ASTM, pellets) 0.9505 0.9491 0.9514 0.9503 0.9512

The present inventors have found that the polymers produced by acatalyst system of the disclosure comprising a metallocene catalystcomponent and a non-metallocene catalyst component possess advantageousproperties in comparison to polymer produced using the metallocenecatalyst alone, and in comparison to conventional polymers.

As used herein, “melt strength” is defined as the force required to drawa molten polymer extrudate at a rate of 12 mm/s² and at an extrusiontemperature (190° C. and 250° C. were used herein) until breakage of theextrudate whereby the force is applied by take up rollers. The polymeris extruded at a velocity of 0.33 mm/s through an annular die of 2 mmdiameter and 30 mm length. Melt strength values reported herein aredetermined using a Gottfert Rheotens tester and are reported incenti-Newtons (cN). Additional experimental parameters for determiningthe melt strength are listed in Table 9. For the measurements of meltstrength, the resins were stabilized with 500 ppm of Irganox 1076 and1500 ppm of Irgafos168.

TABLE 9 Melt Strength test parameters Acceleration 12 mm/s² Temperature190.0° C. Piston diameter 12 mm Piston speed 0.4862 mm/s Die diameter 2mm Die length 30 mm Shear rate at the die 70.0 s⁻¹ Strand length 125.0mm Vo 17.5 mm/s Vs 70.8 mm/s

FIG. 2 shows the melt strength of non-limiting inventive resins 1, 2,and 3 compared with several conventional resins having low MI (BMC-100untailored, BMC-100 tailored, Borouge FB2230, and EZP 1804). As seen inFIG. 2, the melt strength of inventive resin 3 is an order of magnitudehigher than that of linear or long chain branched polyethylenes ofsimilar MI.

It is known in the art that when a polymer is subjected to uniaxialextension, the extensional viscosity of the polymer increases withstrain rate. It is also known that the transient uniaxial extensionalviscosity of a linear polymer can be predicted. “Strain hardening”occurs when a polymer is subjected to uniaxial extension and thetransient extensional viscosity increases more than what is predictedfrom linear viscoelastic theory. As defined herein, the strain hardeningindex is the ratio of the observed transient uniaxial extensionalviscosity (η_(E) ⁺ observed) to the theoretically predicted transientuniaxial extensional viscosity (η_(E) ⁺ predicted). Strain hardeningindex is expressed herein as the following ratio:η_(E) ⁺observed/η_(E) ⁺predicted.

Referring now to FIG. 3 there is provided the extensional viscosity ofinventive resin 3 at a function of time. At conditions characteristic offilm blowing for example strain rate of 1 sec⁻¹, temperature of 190° C.,and time of 4 seconds (i.e., a strain (c) of 4), the strain hardeningindex of the polymers of the present disclosure is a value greater than3 in some embodiments, a value greater than 5 in other embodiments, avalue greater than 8 in even other embodiments, and a value greater than10 in still other embodiments.

For extensional viscosity measurements, the resins were stabilized with500 ppm of Irganox 1076 and 1500 ppm of Irgafos168. The transientuniaxial extensional viscosity was measured at temperatures of 150° C.and 190° C. and different strain rates, 0.1 sec⁻¹, 1.0 sec⁻¹, and 10sec⁻¹. For example, the transient uniaxial extensional viscosity can bemeasured using a SER-HV-401 Testing Platform, which is commerciallyavailable from Xpansion Instruments LLC, Tallmadge, Ohio, USA. The SERTesting Platform was used on a Rheometrics ARES-LS rotational rheometer,which is available from TA Instruments. Inc., Newcastle, Del., USA. TheSER Testing Platform is described in U.S. Pat. No. 6,578,413, which isincorporated herein by reference. A general description of transientuniaxial extensional viscosity measurements is provided, for example in,“Strain hardening of various polyolefins in uniaxial elongational flow”,The Society of Rheology, Inc. J. Rheol. 47(3), 619-630 (2003); and“Measuring the transient extensional rheology of polyethylene meltsusing the SER universal testing platform”, The Society of Rheology, Inc.J. Rheol. 49(3), 585-606 (2005), incorporated herein by reference.

Extensional rheology data from the Sentmanat Extensional Rhoemeter (SER)indicate the inventive resins show strain hardening behavior andextremely high transient uniaxial extensional viscosities (also referredto herein simply as “extensional viscosity”). FIG. 3 shows extensionalviscosity of inventive resin 3 as a function of time. The reference linein FIG. 3 is the predicted linear viscoelastic envelop.

The inventive resins show strong shear thinning. They can be readilyextruded but have very high viscosities at low shear rates, providingfor the high melt strength. FIG. 4 shows the shear thinningcharacteristics of inventive resins 1, 2 and 3 compared to the XCAT-HPbase resin. As can be seen in FIG. 4, the inventive resins have similarviscosities at high frequencies but much higher viscosities at lowfrequencies than the base resin (shear thinning) FIG. 5 comparesinventive resins 1, 2, and 3 with conventional resins (Borouge FB2230and EZP 1804), which show very high/strong shear thinningcharacteristics. As can be seen in FIG. 5, the inventive resins havesimilar viscosities at high frequencies but much higher viscosities atlow frequencies than comparative resins (comparative resins already showvery high shear thinning)

In FIG. 6, the Van Gurp-Palmen plots of non-limiting inventive resins 2and 3 are shown in comparison with the HP-100 base resin. FIG. 7 shows acomparison of the van Gurp-Palmen plots of non-limiting inventive resins2 and 3 and two conventional resins (Borouge FB2230 and EZP 1804).EZP1804 exhibits the signature of a highly branched long-chain LLDPE.Borouge 2230 is a commercial bimodal LLDPE that does not have long chainbranches. Both conventional resins show the expected behavior.

Example 44 Film Products

Despite the high viscosities, the material could readily be made intofilm with good bubble stability. Blown films were made using HaakeRheomex 252P single screw extruder in connection with a Brabender blownfilm die. The extruder was equipped with a 19 mm (0.75 inch) meteringscrew that has a compression ratio 3:1. Ratio of screw diameter overlength was 20:1. Output rate was about 3.5 lbs/hr. Additional filmblowing parameters are provided in Table 10.

TABLE 10 Film Blowing parameters Film Blowing Conditions TemperatureProfile Zone 1 (° C.) 185 Zone 2 (° C.) 185 Zone 3 (° C.) 195 Die (° C.)200 Melt Temperature (° C.) 198 Process Data Output (lb/h) 3.5 HeadPressure (psi) 343 Die Pressure (psi) 2350 Screw Speed (rpm) 32 Gauge(mils) 1

Tables 11 and 12 provide some properties of non-limiting example filmsproduced from resins of the disclosure.

TABLE 11 Film Properties - Resin Density 0.93 Sample ID 00270-136 -011-012 -021 -022 -031 -032 -041 -042 -051 -052 Material: 29 29 30 30 31 3132 32 33 33 Films from resin example MI 1.25 1.254 1.10 1.10 0.91 0.910.73 0.73 0.09 0.089 HLMI 22.32 22.32 21.84 21.84 21.08 21.08 19.3719.37 8.975 8.975 MIR 17.8 17.8 19.9 19.9 23.2 23.2 26.7 26.7 100.8100.8 Density 0.928 0.928 0.929 0.929 0.930 0.930 0.931 0.931 0.9290.929 Film Properties BUR 2.2 3.2 2.2 3.2 2.2 3.2 2.2 3.2 2.2 3 1%Secant Modulus (psi) MD 37695 40501 45924 39999 47090 36373 48140 41123TD 48655 46125 49548 54153 57231 52400 59120 49967 Tensile YieldStrength (psi) MD 1847 1870 1946 2054 2061 1999 2109 2090 1,998 TD 20912069 2268 2309 2461 2493 2395 2435 Elongation @ Yield (%) MD 5.2 5.5 5.56 5.4 5.3 5.4 5.4 5.7 TD 5.3 5.3 5.6 5 5.9 5.6 4.9 5.1 Tensile Strength(psi) MD 6529 6601 5901 6675 6691 6757 7314 7197 8,678 TD 6518 6579 64466840 6499 6637 5855 6837 Elongation @ Break (%) MD 596 628 380 492 454567 386 462 165 TD 704 715 730 701 738 707 717 675 Gloss (GU)* MD 74 6762 55 60 51 37 33 18 15 TD 76 67 60 57 60 48 35 30 19 11 Haze 6 12.410.5 12.5 9.1 13.1 17.4 24.5 45.3 42.4 Clarity 97 96 84.7 86.7 87.2 84.570.5 73.3 40.2 35.5 Transmittance 92.6 92.6 92.6 92.7 92.6 92.8 92.5 7491.9 92.2 Internal Haze 2.06 2.47 1.74 2.26 1.64 1.61 1.24 1.4 0.81 0.97Elmendorf Tear MD (gms) 35.06 56.16 21.84 18.56 19.8 42.28 14.86 24.74TD (gms) 634.4 603.52 589.12 551.52 634.08 570.88 718.08 623.84 MD(gms/mil) 34 57 19 22 19 45 15 27 TD (gms/mil) 560 579 511 592 548 611619 675 Puncture Peak Load (lbs) 10.73 10.76 11.5 8.79 11.36 8.98 10.69.43 Peak Force/mil (lbs/mil) 8.94 10.06 9.5 9.66 9.62 8.89 9.46 10.14Break Energy (inch-lbs) 17.98 23.49 14.79 14.88 15.67 14.44 14.74 16.14Break Energy/mil (inch-lbs/mil) 14.98 21.96 12.22 16.35 13.28 14.2913.16 17.36 Dart Drop gms 119 115.5 117 84 87 70 90 484 gms/mil 99.17107.94 96.69 92.31 73.73 69.31 80.36 90.3 Shrink MD 87 80 89 88 90 88 8986 88 85 TD −18 13 −16 12 −14 21 −8 22 21 24 FAR −10 −30 −20 −20 −20 −20−20 Gauge Mic (mils) Average 1.2 1.07 1.21 0.91 1.18 1.01 1.12 0.93 1.161.02 Low 0.95 0.84 1.05 0.6 0.96 0.56 0.89 0.6 0.51 0.54 High 1.68 1.411.69 1.2 1.49 1.55 1.35 0.93 1.71 1.38

TABLE 12 Film Properties - Resin Density 0.92 Sample ID 00270 128- -128--135- -135- -135- -128-011 -128-021 031 041 -128-051 011 021 022Material: 24 26 27 28 commercial 1a 1b 1c Films from resin controlexample Exceed 1018 CA MI 1.331 0.6933 0.0808 0.093 0.59 0.59 HLMI 22.1713.97 5.5 5.3 13.54 13.54 MIR 16.66 20.15 68.07 56.99 22.95 22.95Density 0.91707 0.91671 0.91721 0.91712 0.91540 0.91636 0.91636 FilmProperties BUR 2.2 3.2 Gauge (mil) 1.41 1.31 1.09 0.92 1.25 Average 1.271.18 0.80 0.72 0.97 0.99 0.96 0.80 Low 1.60 1.46 1.37 1.14 1.53 0.680.76 0.55 High 1.27 1.13 1.21 Elmendorf Tear MD (g) 315 128 24 36 384218 32 62 TD (g) 567 690 755 603 396 331 410 395 MD (g/mil) 255 105 2949 311 233 34 79 TD (g/mil) 451 591 797 674 333 369 416 540 Dart DropMthd A (g) * 301.5 * * * 288 249 225 (g/mil) * 230 * * * 291 259 281Tensile & Elongation Tensile @ Yield (psi) MD 1,129 1,170 1,622 1,3081,227 1,086 1,290 TD 1,244 1,352 1,520 1,420 1,317 1,132 1,227 UltimateTensile (psi) MD 8,404 8,235 10,139 9,593 9,218 8,046 8,793 TD 8,1918,955 9,025 8,402 9,428 8,814 7,329 Elongation @ Yield (%) MD 6.1 6.36.9 6.4 5.8 6.2 5.5 TD 6 5.7 5.2 5.1 5.9 6.1 6.5 Break Elongation (%) MD661 570 311 324 9218 636 559 TD 668 622 622 609 9428 620 486 MD 21,67520,776 27,391 25,079 23,856 19,821 21,395 TD 20,449 22,779 31,745 24,76323,377 18,103 20,055 Puncture Mthd A Peak Force (lb) 15.2 15.7 10.8 14.212.0 9.4 11.6 Peak Force (lb/mil) 10.8 12.0 9.9 15.4 9.6 9.5 12.1 BreakEnergy (in-lb) 51.7 46.9 20.3 31.2 43.3 32.0 28.0 Break Energy 36.7 35.818.6 33.9 34.6 32.3 29.2 (in-lb/mil) Internal Haze (%) average value(%)2.62 0.91 0.64 0.76 5.42 1.06 1.08 Shrink (%) MD 62 81 87 89 30 47 84 81TD 6 −9 3 8 19 8 21 14 GLOSS MD 47 67.7 12.5 19.8 9.4 44.5 42 TD 46.670.1 14.5 16.8 9.6 42.6 37.6 Haze (%) average value (%) 13.9 6.03 50.541.1 66.9 15.0 16.6 *exhausted sample and unable to obtain 10/10 ratio

The phrases, unless otherwise specified, “consists essentially of” and“consisting essentially of” do not exclude the presence of other steps,elements, or materials, whether or not, specifically mentioned in thisspecification, as along as such steps, elements, or materials, do notaffect the basic and novel characteristics of the invention,additionally, they do not exclude impurities normally associated withthe elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted and to theextent such disclosure is consistent with the description of the presentinvention. Further, all documents and references cited herein, includingtesting procedures, publications, patents, journal articles, etc. areherein fully incorporated by reference for all jurisdictions in whichsuch incorporation is permitted and to the extent such disclosure isconsistent with the description of the present invention.

While the invention has been described with respect to a number ofembodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the invention asdisclosed herein.

What is claimed is:
 1. A catalyst system comprising: a first catalystcomponent comprising a metallocene catalyst compound; a second catalystcomponent having the following formula I:

wherein M is Zr; wherein R¹ is selected from CH₂CH₂, (CH₂)₃, (CH₂)₄,CH₂CHMeCH₂, CH₂CMe₂CH₂; wherein R² is a substituted aryl or asubstituted heteroaryl; wherein R⁴ is selected from methyl, ethyl,propyl, butyl, and pentyl; wherein R³ and R⁵ to R⁹ are H; and wherein Xis selected from F, Cl, Br, I, benzyl, or C₁ to C₅ alkyls; andoptionally, a cocatalyst; wherein said metallocene catalyst compound hasa formula selected from the group consisting of Cp^(A)Cp^(B)M′X′_(n),Cp^(A)(A)Cp^(B)M′X′_(n), Cp^(A)(A)QM′X′_(n) and Cp^(A)M′Q_(q)X′_(n),wherein Cp^(A) and Cp^(B) are independently selected from the groupconsisting of cyclopentadienyl ligands and ligands isolobal tocyclopentadienyl, either or both Cp^(A) and Cp^(B) optionally containheteroatoms, and either or both Cp^(A) and Cp^(B) may be substituted byone or more R groups, wherein M′ is selected from the group consistingof Groups 3 through 12 atoms and lanthanide Group atoms, wherein X′ is aleaving group, wherein n is 0 or an integer from 1 to 4, wherein A isselected from the group consisting of divalent alkyls, divalent loweralkyls, divalent substituted alkyls, divalent heteroalkyls, divalentalkenyls, divalent lower alkenyls, divalent substituted alkenyls,divalent heteroalkenyls, divalent alkynyls, divalent lower alkynyls,divalent substituted alkynyls, divalent heteroalkynyls, divalentalkoxys, divalent lower alkoxys, divalent aryloxys, divalent alkylthios,divalent lower alkyl thios, divalent arylthios, divalent aryls, divalentsubstituted aryls, divalent heteroaryls, divalent aralkyls, divalentaralkylenes, divalent alkaryls, divalent alkarylenes, divalenthaloalkyls, divalent haloalkenyls, divalent haloalkynyls, divalentheteroalkyls, divalent heterocycles, divalent heteroaryls, divalentheteroatom-containing groups, divalent hydrocarbyls, divalent lowerhydrocarbyls, divalent substituted hydrocarbyls, divalentheterohydrocarbyls, divalent silyls, divalent boryls, divalentphosphinos, divalent phosphines, divalent aminos, divalent amines,divalent ethers, and divalent thioethers; wherein Q is selected from thegroup consisting of heteroatom-containing ligands, ROO⁻, RO—, R(O)—,—NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, and substituted andunsubstituted aryl groups; wherein R is selected from the groupconsisting of alkyls, lower alkyls, substituted alkyls, heteroalkyls,alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls,alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys,lower alkoxys, aryloxys, alkylthios, lower alkyl thios, arylthios,aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls,alkarylenes, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls,heterocycles, heteroaryls, heteroatom-containing groups, hydrocarbyls,lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls,silyls, boryls, phosphinos, phosphines, aminos, amines, ethers, andthioethers; and wherein q is selected from 0 to 3; and wherein saidsecond catalyst component is present in an amount in a range of fromabout 0.001 to about 5.0 mol % relative to said first catalystcomponent.
 2. The catalyst system of claim 1 wherein said secondcatalyst component is present in an amount in a range of from about 0.05to about 2.5 mol % relative to said first catalyst component.
 3. Thecatalyst system of claim 1 wherein said metallocene catalyst compound isselected from the group consisting of(Pentamethylcyclopentadienyl)(Propyl cyclopentadienyl)ZrX′₂, (Tetramethylcyclopentadienyl)(Propyl cyclopentadienyl)ZrX′₂,(Pentamethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX′₂,(Tetramethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX′₂,Me₂Si(Indenyl)₂ZrX′₂, Me₂Si(Tetrahydroindenyl)₂ZrX′₂, (n-propylcyclopentadienyl)₂ZrX′₂, (n-propyl cyclopentadienyl)₂HfX′₂, (n-butylcyclopentadienyl)₂ZrX′₂, (n-butyl cyclopentadienyl)₂HfX′₂, (1-Methyl,3-Butyl cyclopentadienyl)₂ZrX′₂, HN(CH₂CH₂N(2,4,6-Me₃Phenyl))₂ZrX′₂,HN(CH₂CH₂N(2,3,4,5,6-Me₅Phenyl))₂ZrX′₂, (1-Me,3-Bu-cyclopentadienyl)₂ZrCl₂, (Propylcyclopentadienyl)(Tetramethylcyclopentadienyl)HfCl₂, (Butylcyclopentadienyl)₂ZrCl₂, (Propyl cyclopentadienyl)₂ZrCl₂, (Butylcyclopentadienyl)₂HfCl₂, (Propyl cyclopentadienyl)₂HfCl₂, and anycombinations thereof.
 4. The catalyst system of claim 1 wherein R² is anaryl group with substituents in the 2 and 6 positions.
 5. The catalystsystem of claim 1 wherein each R¹ is either (CH₂)₃ or (CH₂)₄; each R² isselected from the group consisting of 2,6-Me₂Ph, 2,6-Et₂Ph, 2,6-Pr₂-Ph,2,6-Bu₂Ph, 2-MeNapthyl, 2,4,6-Me₃Ph, 2,4,6-Et₃Ph, 2,4,6-Pr₃Ph, andcarbazole; each R⁴ is selected from the group consisting of Methyl andButyl; and X is selected from the group consisting of F, Cl, and Me. 6.The catalyst system of claim 5 wherein R¹ is (CH₂)₃; each R² is either2,4,6-Me3Ph or 2-MeNapthyl; each R⁴ is CH₃; X is Cl.
 7. The catalystsystem of claim 1 wherein said cocatalyst includes an activator and, thecatalyst system optionally includes a support.
 8. The catalyst system ofclaim 7 wherein said activator is methylaluminoxane and said support issilica.
 9. A method for making the catalyst system of claim 1comprising: contacting in a diluent (a) the first catalyst component;and (b) the second catalyst component, and (c) a cocatalyst to form thecatalyst system.
 10. The method of claim 9 wherein said diluent isselected from the group consisting of pentane, isopentane, hexane,isohexane, heptane, octane, nonane, cyclopentane, cyclohexane, benzene,toluene, ethylbenzene and diethylbenzene.
 11. A method for olefinpolymerization comprising: contacting one or more olefin monomers withthe catalyst system of claim 1 under olefin polymerization conditions tocreate a polyolefin, wherein said first catalyst component producespolymer having a weight average molecular weight (Mw) in the range offrom 40,000 to 200,000 g/mol, and said second catalyst componentproduces polymer having an Mw of greater than 1,000,000 g/mol.
 12. Themethod of claim 11 wherein said olefin monomers comprise ethylene, andoptionally, hexene, butene, octene, or mixtures thereof.
 13. The methodof claim 11 wherein said olefin monomers further comprise at least onecomonomer species selected from the group consisting of propylene,1-butene, t-pentene, 1-hexene, 1-heptene, 1-octene, and combinationsthereof.
 14. The method of claim 11 wherein said contacting is in agas-phase, slurry-phase or solution-phase reactor.